Refrigerant, heat transfer compositions, methods, and systems

ABSTRACT

Disclosed are refrigerants, and heat transfer compositions, heat transfer systems and heat transfer methods containing such refrigerants, wherein the refrigerant comprises at least about 97% by weight of the following three components (a)-(c) and the following fourth component if present:
     (a) trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),   (b) trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),   (c) trifluoroiodomethane (CF3I), and.   (d) 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea).

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. application Ser. No.16/877,829, filed May 19, 2020, Now pending, which is a continuation ofU.S. application Ser. No. 15/870,597, filed Jan. 12, 2018, (now U.S.Pat. No. 10,655,040, issued May 19, 2020) which application claims thepriority benefit of each of U.S. Provisional Application Nos. 62/445,800and 62/445,816, each of which was filed on Jan. 13, 2017, and each ofwhich is incorporated herein by reference.

The present application also claims the priority benefit of each of USProvisional Application Nos. 62/522,836; 62,522,846; 62/522,851; and62/522,860, each of which was filed on Jun. 21, 2017 and each of whichis incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to compositions, methods and systemshaving utility in a heat exchange system, including refrigerationapplications and in particular aspects to compositions for replacementof the refrigerant R-134a for heating and cooling applications and toretrofitting heat exchange systems, including systems which containR-134a.

BACKGROUND

Mechanical refrigeration systems, and related heat transfer devices,such as heat pumps and air conditioners, using refrigerant liquids arewell known in the art for industrial, commercial and domestic uses.Chlorofluorocarbons (CFCs) were developed in the 1930s as refrigerantsfor such systems. However, since the 1980s the effect of CFCs on thestratospheric ozone layer has become the focus of much attention. In1987, a number of governments signed the Montreal Protocol to protectthe global environment, setting forth a timetable for phasing out theCFC products. CFCs were replaced with more environmentally acceptablematerials that contain hydrogen, namely the hydrochlorofluorocarbons(HCFCs).

One of the most commonly used hydrochlorofluorocarbon refrigerants waschlorodifluoromethane (HCFC-22). However, subsequent amendments to theMontreal protocol accelerated the phase out of the CFCs and alsoscheduled the phase-out of HCFCs, including HCFC-22.

In response to the requirement for a non-flammable, non-toxicalternative to the CFCs and HCFCs, industry has developed a number ofhydrofluorocarbons (HFCs) which have zero ozone depletion potential.R-134a (1,1,1,2-tetrafluoroethane) was adopted for various heat exchangeapplications, including refrigeration applications such as mediumtemperature refrigeration systems and vending machines, as well as heatpumps and chillers, as it does not contribute to ozone depletion.

However, R-134a has a Global Warming Potential (GWP) of about 1430(according to IPCC (2007) Climate Change 2007: The Physical ScienceBasis. Contribution of Working Group I to the Fourth Assessment Reportof the Intergovernmental Panel on Climate Change. S.

Solomon et al, Cambridge University Press. Cambridge, United Kingdomp996). There is therefore a need in the art for the replacement ofR-134a with a more environmentally acceptable alternative.

It is understood in the art that replacement heat transfer fluids mustpossess a mosaic of properties depending on the particular application.For many of the applications which involve the cooling or heat of air towhich members of public are intended to be exposed, that mosaic willgenerally include excellent heat transfer properties, chemicalstability, low or no toxicity, non-flammability and/or lubricantcompatibility amongst others. The identification of a heat transferfluid meeting all of these requirements is not trivial.

Non-flammability is considered to be an important, and in some cases, anessential property for many heat transfer applications Thus, it isfrequently beneficial to use compounds in such compositions, which arenon-flammable. As used herein, the term “non-flammable” refers tocompounds or compositions which are determined to be non-flammable inaccordance with ASTM standard E-681-2001 at conditions described inASHRAE Standard 34-2013 and described in Appendix 1 to ASHRAE Standard34-2013.

However, non-flammabillity is generally understood to be inverselycorrelated to low GWP.

For example, while R-134a is classed as a non-flammable (i.e. class 1)refrigerant, it has a high GWP of about 1430. In contrast, while R152a(1,1-difluoroethane) has a GWP of about 124, it is classed as aflamamable (i.e. a class 2) refrigerant. Thus, it is generally difficultto provide a refrigerant which is non-flammable, and which has a lowGWP, that is, a GWP of not greater than about 150.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A shows an example of a previously used R-134a refrigerationsystem;

FIG. 1B shows an example of a R-134a refrigeration system that is thebasis for the comparative examples described herein.

FIG. 2 shows a cascaded refrigeration system according to preferredembodiments of the invention;

FIG. 3 shows an alternative cascaded refrigeration system according topreferred embodiments of the invention;

FIG. 4 shows an alternative cascaded refrigeration system according toembodiments of the invention; and

FIG. 5 shows an alternative cascaded refrigeration system according toembodiments of the invention.

SUMMARY OF THE INVENTION

Applicants have found that the compositions of the present inventionsatisfy in an exceptional and unexpected way the need for alternativesand/or replacements and/or retrofits for refrigerants in suchapplications, particularly and preferably HFC-134a (also referred toherein as “R-134a”) that at once have lower GWP values and providenon-flammable, non-toxic fluids that have a close match in coolingefficiency and capacity to R-134a in refrigeration applications in suchsystems.

The present invention includes refrigerants comprising at least about97% by weight of the following three compounds, with each compound beingpresent in the following relative percentages:

from 1% by weight to 2%+/−0.5% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),

from about 77% by weight to about 83% by weighttrans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), and from about 15% byweight to about 21% by weight trifluoroiodomethane (CF₃I).

Refrigerants as described in this paragraph are sometimes referred tofor convenience as Refrigerant 1.

As used herein with respect to percentages based on a list of compoundsor components, the term “relative percentages” means the percentage ofthe identified comounds or components based on the total weight of thelisted components.

As used herein with respect to weight percentages, the term “about” inrelation to the amounts expressed in weight percent means that theamount of the component can vary by an amount of +/−2% by weight. Theamount of the component is preferably +/−1% by weight, more preferably+/−0.5% by weight, even more preferably +/−0.3% by weight, and mostpreferably +/−0.2% by weight. The refrigerants and compositions of theinvention include in preferred embodiments amounts of an identifiedcompound or component specficied as being “about” wherein the amount isthe identified amount +/−1% by weight, and even more preferably +/−0.5%by weight.

The present invention includes refrigerants comprising at least about98.5% by weight of the following three compounds, with each compoundbeing present in the following relative percentages:

from 1% by weight to 2%+/−0.5% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),

from about 77% by weight to about 83% by weighttrans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), and

from about 15% by weight to about 21% by weight trifluoroiodomethane(CF₃I).

Refrigerants as described in this paragraph are sometimes referred tofor convenience as Refrigerant 2.

The present invention includes refrigerants comprising at least about99.5% by weight of the following three compounds, with each compoundbeing present in the following relative percentages:

from 1% by weight to 2%+/−0.5% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),

from about 77% by weight to about 83% by weighttrans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), and

from about 15% by weight to about 21% by weight trifluoroiodomethane(CF₃I).

Refrigerants as described in this paragraph are sometimes referred tofor convenience as Refrigerant 3.

The present invention includes refrigerants consisting essentially ofthe following three compounds, with each compound being present in thefollowing relative percentages:

from 1% by weight to 2%+/−0.5% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),

from about 77% by weight to about 83% by weighttrans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), and

from about 15% by weight to about 21% by weight trifluoroiodomethane(CF₃I).

Refrigerants as described in this paragraph are sometimes referred tofor convenience as Refrigerant 4.

The present invention includes refrigerants consisting of the followingfour compounds, with each compound being present in the followingrelative percentages:

from 1% by weight to 2%+/−0.5% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),

from about 77% by weight to about 83% by weighttrans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), and

from about 15% by weight to about 21% by weight trifluoroiodomethane(CF₃I).

Refrigerants as described in this paragraph are sometimes referred tofor convenience as Refrigerant 5.

The present invention includes refrigerants comprising at least about97% by weight of the following three compounds, with each compound beingpresent in the following relative percentages:

2%+/−0.5% by weight trans-1-chloro-3,3,3-trifluoropropene(HFCO-1233zd(E)),

about 78% by weight of trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),and

about 20% by weight trifluoroiodomethane (CF3I). Refrigerants asdescribed in this paragraph are sometimes referred to for convenience asRefrigerant 6.

The present invention includes refrigerants comprising at least about98.5% by weight of the following three compounds, with each compoundbeing present in the following relative percentages:

2%+/−0.5% by weight trans-1-chloro-3,3,3-trifluoropropene(HFCO-1233zd(E)),

about 78% by weight of trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),and

about 20% by weight trifluoroiodomethane (CF3I). Refrigerants asdescribed in this paragraph are sometimes referred to for convenience asRefrigerant 7.

The present invention includes refrigerants consisting essentially ofthe following three compounds, with each compound being present in thefollowing relative percentages: 2%+/−0.5% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)), about 78% byweight of trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), and about20% by weight trifluoroiodomethane (CF3I). Refrigerants as described inthis paragraph are sometimes referred to for convenience as Refrigerant8.

The present invention includes refrigerants consisting of the followingthree compounds, with each compound being present in the followingrelative percentages: 2%+/−0.5% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)), about 78% byweight of trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), and about20% by weight trifluoroiodomethane (CF3I). Refrigerants as described inthis paragraph are sometimes referred to for convenience as Refrigerant9.

The present invention includes refrigerants comprising at least about98.5% by weight of the following three compounds, with each compoundbeing present in the following relative percentages:

2%+/−0.5% by weight trans-1-chloro-3,3,3-trifluoropropene(HFCO-1233zd(E)),

78%+/−0.5% by weight of trans-1,3,3,3-tetrafluoropropene(HFO-1234ze(E)), and

20%+/−0.5% by weight trifluoroiodomethane (CF3I). Refrigerants asdescribed in this paragraph are sometimes referred to for convenience asRefrigerant 10.

The present invention includes refrigerants consisting essentially ofthe following three compounds, with each compound being present in thefollowing relative percentages:

2%+/−0.5% by weight trans-1-chloro-3,3,3-trifluoropropene(HFCO-1233zd(E)),

78%+/−0.5% by weight of trans-1,3,3,3-tetrafluoropropene(HFO-1234ze(E)), and

20%+/−0.5% by weight trifluoroiodomethane (CF3I). Refrigerants asdescribed in this paragraph are sometimes referred to for convenience asRefrigerant 11.

The present invention includes refrigerants consisting of the followingthree compounds, with each compound being present in the followingrelative percentages:

2%+/−0.5% by weight trans-1-chloro-3,3,3-trifluoropropene(HFCO-1233zd(E)),

78%+/−0.5% by weight of trans-1,3,3,3-tetrafluoropropene(HFO-1234ze(E)), and

20%+/−0.5% by weight trifluoroiodomethane (CF3I). Refrigerants asdescribed in this paragraph are sometimes referred to for convenience asRefrigerant 12.

The present invention includes refrigerants comprising at least about97% by weight of the following four compounds, with each compound beingpresent in the following relative percentages:

from 1% by weight to 2%+/−0.5% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),

from about 73% by weight to about 87% by weighttrans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),

4.4%+/−0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and

from about 6.6% by weight to about 20.6% by weight trifluoroiodomethane(CF₃I).

Refrigerants as described in this paragraph are sometimes referred tofor convenience as Refrigerant 13.

The present invention includes refrigerants comprising at least about98.5% by weight of the following three compounds, with each compoundbeing present in the following relative percentages:

from 1% by weight to 2%+/−0.5% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),

from about 73% by weight to about 87% by weighttrans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 4.4%+/−0.5% by weight1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and

from about 6.6% by weight to about 20.6% by weight trifluoroiodomethane(CF3I).

Refrigerants as described in this paragraph are sometimes referred tofor convenience as Refrigerant 14.

The present invention includes refrigerants comprising at least about99.5% by weight of the following three compounds, with each compoundbeing present in the following relative percentages:

from 1% by weight to 2%+/−0.5% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),

from about 73% by weight to about 87% by weighttrans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 4.4%+/−0.5% by weight1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and

from about 6.6% by weight to about 20.6% by weight trifluoroiodomethane(CF₃I).

Refrigerants as described in this paragraph are sometimes referred tofor convenience as Refrigerant 15.

The present invention includes refrigerants consisting essentially ofthe following four compounds, with each compound being present in thefollowing relative percentages:

from 1% by weight to 2%+/−0.5% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),

from about 73% by weight to about 87% by weighttrans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),

4.4%+/−0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and

from about 6.6% by weight to about 20.6% by weight trifluoroiodomethane(CF₃I).

Refrigerants as described in this paragraph are sometimes referred tofor convenience as Refrigerant 16.

The present invention includes refrigerants consisting of the followingfour compounds, with each compound being present in the followingrelative percentages:

from 1% by weight to 2%+/−0.5% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),

from about 73% by weight to about 87% by weighttrans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 4.4%+/−0.5% by weight1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and

from about 6.6% by weight to about 20.6% by weight trifluoroiodomethane(CF₃I).

Refrigerants as described in this paragraph are sometimes referred tofor convenience as Refrigerant 17.

The present invention includes refrigerants comprising at least about98.5% by weight of the following four compounds, with each compoundbeing present in the following relative percentages:

2%+/−0.5% by weight trans-1-chloro-3,3,3-trifluoropropene(HFCO-1233zd(E)),

about 84% by weight trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),

4.4%+/−0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and

about 9.6% by weight trifluoroiodomethane (CF3I). Refrigerants asdescribed in this paragraph are sometimes referred to for convenience asRefrigerant 18.

The present invention includes refrigerants consisting essentially ofthe following four compounds, with each compound being present in thefollowing relative percentages:

2%+/−0.5% by weight trans-1-chloro-3,3,3-trifluoropropene(HFCO-1233zd(E)),

about 84% by weight trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),

4.4%+/−0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), andabout 9.6% by weight trifluoroiodomethane (CF3I). Refrigerants asdescribed in this paragraph are sometimes referred to for convenience asRefrigerant 19.

The present invention includes refrigerants consisting of the followingfour compounds, with each compound being present in the followingrelative percentages:

2%+/−0.5% by weight trans-1-chloro-3,3,3-trifluoropropene(HFCO-1233zd(E)),

about 84% by weight trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),

4.4%+/−0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and

about 9.6% by weight trifluoroiodomethane (CF3I). Refrigerants asdescribed in this paragraph are sometimes referred to for convenience asRefrigerant 20.

The present invention includes refrigerants comprising at least about98.5% by weight of the following four compounds, with each compoundbeing present in the following relative percentages:

2%+/−0.5% by weight trans-1-chloro-3,3,3-trifluoropropene(HFCO-1233zd(E)),

84%+/−0.5% by weight trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),

4.4%+/−0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and

9.6%+/−0.5% by weight trifluoroiodomethane (CF3I). Refrigerants asdescribed in this paragraph are sometimes referred to for convenience asRefrigerant 21.

The present invention includes refrigerants consisting essentially ofthe following four compounds, with each compound being present in thefollowing relative percentages:

2%+/−0.5% by weight trans-1-chloro-3,3,3-trifluoropropene(HFCO-1233zd(E)),

84%+/−0.5% by weight trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),

4.4%+/−0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and

9.6%+/−0.5% by weight trifluoroiodomethane (CF3I). Refrigerants asdescribed in this paragraph are sometimes referred to for convenience asRefrigerant 22.

The present invention includes refrigerants consisting of the followingfour compounds, with each compound being present in the followingrelative percentages:

2%+/−0.5% by weight trans-1-chloro-3,3,3-trifluoropropene(HFCO-1233zd(E)),

84%+/−0.5% by weight trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),

4.4%+/−0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and

9.6%+/−0.5% by weight trifluoroiodomethane (CF3I). Refrigerants asdescribed in this paragraph are sometimes referred to for convenience asRefrigerant 23.

The present invention also provides refrigerant compositions in whichthe refrigerant is non-flammable. As used herein, the term“non-flammable” refers to compounds or compositions which are determinedto be non-flammable in accordance with ASTM standard E-681-2016 atconditions described in Appendix 1 to ASHRAE Standard 34-2016. Inparticular, the present invention provides each of the refrigerants asidentified herein as Refrigerants 1-23 in which the refrigerant isnon-flammable, and for the purposes of convenience, each suchrefrigerant is referred to herein as Refrigerant 1NF, Refrigerant 2NF,Refrigerant 3NF, (and through to) Refrigerant 23NF, respectively.

The present invention also provides refrigerant compositions in whichthe refrigerant has a Global Warming Potential (GWP) of 150 or less. Inparticular, the present invention provides each of the refrigerants asidentified herein as Refrigerants 1-23 in which the refrigerant has aGWP of 150 or less, and for the purposes of convenience, each suchrefrigerant is referred to herein as Refrigerant 1GWP150, Refrigerant2GWP150, Refrigerant 3GWP150, (and through to) Refrigerant 23GWP150,respectively.

The phrase “Global Warming Potential” (hereinafter “GWP”) was developedto allow comparisons of the global warming impact of different gases.Specifically, it is a measure of how much energy the emission of one tonof a gas will absorb over a given period of time, relative to theemission of one ton of carbon dioxide. The larger the GWP, the more thata given gas warms the Earth compared to CO₂ over that time period. Thetime period usually used for GWP is 100 years. GWP provides a commonmeasure, which allows analysts to add up emission estimates of differentgases. See www.epa.gov.

The present invention also provides refrigerant compositions in whichthe refrigerant has a Global Warming Potential (GWP) of less than 150and in which the refrigerant is non-flammable. In particular, thepresent invention provides each of the refrigerants as identified hereinas Refrigerants 1-23 in which the refrigerant is non-flammable and has aGWP of less than 150, and for the purposes of convenience, each suchrefrigerant is referred to herein as Refrigerant 1NFGWP150, Refrigerant2NFGWP150, Refrigerant 3NFGWP150, (and through to) Refrigerant23NFGWP150, respectively.

The present invention also provides refrigerant compositions in whichthe refrigerant has a Global Warming Potential (GWP) of 5 or less. Inparticular, the present invention provides each of the refrigerants asidentified herein as Refrigerants 1-12 in which the refrigerant has aGWP of 5 or less, and for the purposes of convenience, each suchrefrigerant is referred to herein as Refrigerant 1GWP5, Refrigerant2GWP5, Refrigerant 3GWP5, (and through to) Refrigerant 12GWP5,respectively.

The present invention also provides refrigerant compositions in whichthe refrigerant is non-flammable and has a Global Warming Potential(GWP) of 5. In particular, the present invention provides each of therefrigerants as identified herein as Refrigerants 1-12 in which therefrigerant has a GWP of 5 or less and in which the refrigerant isnon-flammable, and for the purposes of convenience, each suchrefrigerant is referred to herein as Refrigerant 1NFGWP5, Refrigerant2NFGWP5, Refrigerant 3NFGWP5, (and through to) Refrigerant 12NFGWP5,respectively.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to refrigerants, heat transfercompositions and heat transfer methods which include or utilizerefrigerant comprising HFCO-1233zd(E), HFO-1234ze(E),trifluoroiodomethane (CF3I). Trifluoroiodomethane (CF3I) is readilyavailable from a variety of commercial sources, including MathesonTriGas, Inc. HFCO-1233zd(E) and HFO-1234ze(E) are commercially availablematerials that can be obtained from Honeywell International, Inc.

Embodiments of the present invention include also refrigerants thatinclude HFC-227ea, in addition to HFCO-1233zd(E), HFO-1234ze(E) andtrifluoroiodomethane (CF3I). HFC-227ea is also a known commerciallyavailable material.

Refrigerants

Applicants have found that refrigerants of the present invention arecapable of providing exceptionally advantageous properties including:heat transfer properties, chemical stability, low or no toxicity,non-flammability, near zero ozone depletion potential (“ODP”), andlubricant compatibility in combination with a low GWP. A particularadvantage of the refrigerants of the present invention is that they arenon-flammable when tested in accordance with the non-flammability testdefined herein. It will be appreciated by the skilled person that theflammability of a refrigerant is an important characteristic for use incertain important heat transfer applications. Thus, it is a desire inthe art to provide a refrigerant composition which can be used as areplacement for and/or as a retrofit for R-134a for refrigerationapplications which has excellent heat transfer properties, chemicalstability, low or no toxicity, near zero ODP, and lubricantcompatibility and which maintains non-flammability in use. Thisrequirement is met by the refrigerants of the present invention.

The Applicants have found that the compositions of the invention arecapable of achieving a difficult to achieve combination of propertiesincluding particularly low GWP. Thus, the compositions of the inventionpreferably have a GWP of 150 or less, or 5 or less.

In addition, the compositions of the invention have a low ODP. Thus, thecompositions of the invention have an ODP of not greater than 0.05,preferably not greater than 0.02, and more preferably about zero.

In addition, the compositions of the invention show acceptable toxicityand preferably have an Occupational Exposure Limit (“OEL”) of greaterthan about 400. As used herein, the term “Occupational Exposure Limit(OEL)” is used in accordance with and has a value determined inaccordance with ASHRAE Standard 34-2016 Designation and SafetyClassification of Refrigerants.

Heat Transfer Compositions

Preferably, the invention includes heat transfer compositions comprisingany one of the refrigerants of the present invention, including inparticular each of Refrigerants 1-23, Refrigerants 1NF-23NF,Refrigerants 1GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150,Refrigerants 1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, in anamount of greater than 40% by weight of the heat transfer composition,or greater than about 50% by weight of the heat transfer composition, orgreater than 70% by weight of the heat transfer composition, or greaterthan 80% by weight of the heat transfer composition or greater than 90%by weight of the heat transfer composition. The heat transfercomposition may consist essentially of or consist of the refrigerant,including in particular each of Refrigerants 1-23, Refrigerants1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5.

The heat transfer compositions of the invention may include othercomponents for the purpose of enhancing or providing certainfunctionality to the compositions. Such other components may include oneor more of lubricants, dyes, solubilizing agents, compatibilizers,stabilizers, antioxidants, corrosion inhibitors, extreme pressureadditives and anti wear additives.

In preferred embodiments the heat transfer compositions comprise any oneof the refrigerants of the present invention, including in particularany one of Refrigerants 1-23, Refrigerants 1NF-23NF, Refrigerants1GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5 and a stabilizer.

In preferred embodiments the heat transfer compositions consistessentially of any one of the refrigerants of the present invention,including in particular any one of Refrigerants 1-23, Refrigerants1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5 and a stabilizer.

In preferred embodiments the heat transfer compositions comprise any oneof the refrigerants of the present invention, including in particularany one of Refrigerants 1-23, Refrigerants 1NF-23NF, Refrigerants1GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5 and a lubricant.

In preferred embodiments the heat transfer compositions consistessentially of any one of the refrigerants of the present invention,including in particular any one of Refrigerants 1-23, Refrigerants1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5 and a lubricant.

In preferred embodiments the heat transfer compositions comprise any oneof the refrigerants of the present invention, including in particularany one of Refrigerants 1-23, Refrigerants 1NF-23NF, Refrigerants1GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, a stabilizer and alubricant.

In preferred embodiments the heat transfer compositions consistessentially of any one of the refrigerants of the present invention,including in particular any one of Refrigerants 1-23, Refrigerants1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, a stabilizer and a lubricant.

Stabilizers

Examples of useful stabilizers for use in the heat transfer compostionshereof include diene-based compounds and/or phenol-based compoundsand/or phosphorus compounds and/or nitrogen compounds and/or epoxides.Examples of preferred stabilizers include diene-based compounds and/orphenol-based compounds and/or phosphorus compounds.

The stabilizer preferably is provided in the heat transfer compositionin an amount of greater than 0 and preferably from 0.0001% by weight toabout 5% by weight, preferably 0.01% by weight to about 2% by weight,and more preferably from 0.1 to about 1% by weight. In each case,percentage by weight refers to the weight of the heat transfercomposition.

The diene-based compounds include C3 to C15 dienes and to compoundsformed by reaction of any two or more C3 to C4 dienes. Preferably, thediene based compounds are selected from the group consisting of allylethers, propadiene, butadiene, isoprene, and terpenes. The diene-basedcompounds are preferably terpenes, which include but are not limited toterebene, retinal, geraniol, terpinene, delta-3 carene, terpinolene,phellandrene, fenchene, myrcene, farnesene, pinene, nerol, citral,camphor, menthol, limonene, nerolidol, phytol, carnosic acid, andvitamin A₁. Preferably, the stabilizer is farnesene. Preferred terpenestabilizers are disclosed in U.S. Provisional Patent Application No.60/638,003 filed on Dec. 12, 2004, published as US 2006/0167044A1, whichis incorporated herein by reference.

In addition, the diene based compounds can be provided in the heattransfer composition in an amount greater than 0 and preferably from0.0001% by weight to about 5% by weight, preferably 0.001% by weight toabout 2.5% by weight, and more preferably from 0.01% to about 1% byweight. In each case, percentage by weight refers to the weight of theheat transfer composition.

The diene based compounds are preferably provided in combination with aphosphorous compound.

The phenol can be one or more compounds selected from4,4′-methylenebis(2,6-di-tert-butylphenol);4,4′-bis(2,6-di-tert-butylphenol); 2,2- or 4,4-biphenyldiols, including4,4′-bis(2-methyl-6-tert-butylphenol); derivatives of 2,2- or4,4-biphenyldiols; 2,2′-methylenebis(4-ethyl-6-tertbutylphenol);2,2′-methylenebis(4-methyl-6-tert-butylphenol);4,4-butylidenebis(3-methyl-6-tert-butylphenol);4,4-isopropylidenebis(2,6-di-tert-butylphenol);2,2′-methylenebis(4-methyl-6-nonylphenol);2,2′-isobutylidenebis(4,6-dimethylphenol);2,2′-methylenebis(4-methyl-6-cyclohexylphenol);2,6-di-tert-butyl-4-methylphenol (BHT); 2,6-di-tert-butyl-4-ethylphenol:2,4-dimethyl-6-tert-butylphenol;2,6-di-tert-alpha-dimethylamino-p-cresol;2,6-di-tert-butyl-4(N,N′-dimethylaminomethylphenol);4,4′-thiobis(2-methyl-6-tert-butylphenol);4,4′-thiobis(3-methyl-6-tert-butylphenol);2,2′-thiobis(4-methyl-6-tert-butylphenol);bis(3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide; bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, tocopherol, hydroquinone,2,2′6,6′-tetra-tert-butyl-4,4′-methylenediphenol and t-butylhydroquinone, and preferably BHT.

The phenol compounds can be provided in the heat transfer composition inan amount of greater than 0 and preferably from 0.0001% by weight toabout 5% by weight, preferably 0.001% by weight to about 2.5% by weight,and more preferably from 0.01% to about 1% by weight. In each case,percentage by weight refers to the weight of the heat transfercomposition.

The phosphorus compound can be a phosphite or a phosphate compound. Forthe purposes of this invention, the phosphite compound can be a diaryl,dialkyl, triaryl and/or trialkyl phosphite, and/or a mixed aryl/alkyldi- or tri-substituted phosphite, in particular one or more compoundsselected from hindered phosphites, tris-(di-tert-butylphenyl)phosphite,di-n-octyl phophite, iso-octyl diphenyl phosphite, iso-decyl diphenylphosphite, tri-iso-decyl phosphate, triphenyl phosphite and diphenylphosphite, particularly diphenyl phosphite.

The phosphate compounds can be a triaryl phosphate, trialkyl phosphate,alkyl mono acid phosphate, aryl diacid phosphate, amine phosphate,preferably triaryl phosphate and/or a trialkyl phosphate, particularlytri-n-butyl phosphate.

The phosphorus compounds can be provided in the heat transfercomposition in an amount of greater than 0 and preferably from 0.0001%by weight to about 5% by weight, preferably 0.001% by weight to about2.5% by weight, and more preferably from 0.01% to about 1% by weight. Ineach case, by weight refers to weight of the heat transfer composition.

When the stabilizer is a nitrogen compound, the stabilizer may comprisean amine based compound such as one or more secondary or tertiary aminesselected from diphenylamine, p-phenylenediamine, triethylamine,tributylamine, diisopropylamine, triisopropylamine and triisobutylamine.The amine based compound can be an amine antioxidant such as asubstituted piperidine compound, i.e. a derivative of an alkylsubstituted piperidyl, piperidinyl, piperazinone, or alkyoxypiperidinyl,particularly one or more amine antioxidants selected from2,2,6,6-tetramethyl-4-piperidone, 2,2,6,6-tetramethyl-4-piperidinol;bis-(1,2,2,6,6-pentamethylpiperidyl)sebacate;di(2,2,6,6-tetramethyl-4-piperidyl)sebacate,poly(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidyl succinate;alkylated paraphenylenediamines such asN-phenyl-N′-(1,3-dimethyl-butyl)-p-phenylenediamine orN,N′-di-sec-butyl-p-phenylenediamine and hydroxylamines such as tallowamines, methyl bis tallow amine and bis tallow amine, orphenol-alpha-napththylamine or Tinuvin®765 (Ciba), BLS®1944 (Mayzo Inc)and BLS® 1770 (Mayzo Inc). For the purposes of this invention, the aminebased compound also can be an alkyldiphenyl amine such as bis(nonylphenyl amine), dialkylamine such as(N-(1-methylethyl)-2-propylamine, or one or more ofphenyl-alpha-naphthyl amine (PANA), alkyl-phenyl-alpha-naphthyl-amine(APANA), and bis (nonylphenyl) amine. Preferably the amine basedcompound is one or more of phenyl-alpha-naphthyl amine (PANA),alkyl-phenyl-alpha-naphthyl-amine (APANA) and bis (nonylphenyl) amine,amd more preferably phenyl-alpha-naphthyl amine (PANA).

Alternatively, or in addition to the nitrogen compounds identifiedabove, one or more compounds selected from dinitrobenzene, nitrobenzene,nitromethane, nitrosobenzene, and TEMPO[(2,2,6,6-tetramethylpiperidin-1-yl)oxyl] may be used as the stabilizer.

The nitrogen compounds can be provided in the heat transfer compositionin an amount of greater than 0 and from 0.0001% by weight to about 5% byweight, preferably 0.001% by weight to about 2.5% by weight, and morepreferably from 0.01% to about 1% by weight. In each case, percentage byweight refers to the weight of the heat transfer composition.

Useful epoxides include aromatic epoxides, alkyl epoxides, and alkyenylepoxides.

The diene based compounds are preferably provided in combination with aphosphorous compound. Preferably, the heat transfer compositioncomprises a refrigerant as set out above and a stabilizer compositioncomprising farnesene and a phosphorous compound selected from a diarylphosphite, a dialkyl phosphite, a triaryl phosphate or a trialkylphosphate, more preferably diphenyl phosphite and/or tri-n-butylphosphate. More preferably the heat transfer composition comprises arefrigerant as described herein and a stabilizer composition comprisingfarnesene and one or more of a diaryl phosphite or a dialkyl phosphite,more preferably diphenyl phosphite. Preferably the stabilizer comprisesfarnesene and diphenyl phosphite.

The heat transfer composition of the invention can preferably compriseRefrigerant 1 and a stabilizer composition comprising BHT, wherein saidBHT is present in an amount of from about 0.0001% by weight to about 5%by weight based on the weight of heat transfer composition. BHT presentin an amount of from about 0.0001% by weight to about 5% by weight basedon the weight of heat transfer composition is sometimes referred to forconvenience as Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 2 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 3 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 4 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 5 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 6 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 7 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 8 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 9 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 10 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 11 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 12 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 13 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 14 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 15 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 16 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 17 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 18 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 19 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 20 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 21 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 22 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 23 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseany of Refrigerants 1NF-23NF and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseany of Refrigerants 1NFGWP150-23NFGWP150 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseany of Refrigerants 1GWP5-12GWP5 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseany of Refrigerants 1NFGWP5-12NFGWP5 and Stabilizer 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 1 and a stabilizer composition comprising farnesene,diphenyl phosphite and BHT, wherein the farnesene is provided in anamount of from about 0.0001% by weight to about 5% by weight based onthe weight of the heat transfer composition, the diphenyl phosphite isprovided in an amount of from about 0.0001% by weight to about 5% byweight based on the weight of the heat transfer composition, and the BHTis provided in an amount of from about 0.0001% by weight to about 5% byweight based on the weight of heat transfer composition. A stabilizercomposition comprising farnesene, diphenyl phosphite and BHT, whereinthe farnesene is provided in an amount of from about 0.0001% by weightto about 5% by weight based on the weight of the heat transfercomposition, the diphenyl phosphite is provided in an amount of fromabout 0.0001% by weight to about 5% by weight based on the weight of theheat transfer composition, and the BHT is provided in an amount of fromabout 0.0001% by weight to about 5% by weight based on the weight ofheat transfer composition is sometimes referred to for convenience asStabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 2 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 3 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 4 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 5 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 6 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 7 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 8 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 9 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 10 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 11 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 12 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 13 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 14 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 15 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 16 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 17 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 18 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 19 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 20 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 21 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 22 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseRefrigerant 23 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseany of Refrigerants 1NF-23NF and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseany of Refrigerants 1NFGWP150-23NFGWP150 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseany of Refrigerants 1GWP5-12GWP5 and Stabilizer 2.

The heat transfer composition of the invention can preferably compriseany of Refrigerants 1NFGWP5-12NFGWP5 and Stabilizer 2.

The heat transfer composition of the invention can more preferablycomprise any one of the refrigerants of the invention as describedherein, including in particular any one of Refrigerants 1-23,Refrigerants 1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, and a stabilizer composition comprising farnesene,diphenyl phosphite and BHT, wherein the farnesene is provided in anamount of from about 0.001% by weight to about 2.5% by weight based onthe weight of the heat transfer composition, the diphenyl phosphite isprovided in an amount of from about 0.001% by weight to about 2.5% byweight based on the weight of the heat transfer composition, and the BHTis provided in an amount of from about 0.001% by weight to about 2.5% byweight based on the weight of heat transfer composition.

The heat transfer composition of the invention can most preferablycomprise any one of the inventive refrigerants, including in particularany one of Refrigerants 1-23, Refrigerants 1NF-23NF, Refrigerants1GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants1GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5, and a stabilizercomposition comprising farnesene, diphenyl phosphite and BHT, whereinthe farnesene is provided in an amount of from about 0.01% by weight toabout 1% by weight based on the weight of the heat transfer composition,the diphenyl phosphite is provided in an amount of from about 0.01% byweight to about 1% by weight based on the weight of the heat transfercomposition, and the BHT is provided in an amount of from about 0.01% byweight to about 1% by weight based on the weight of heat transfercomposition.

Lubricants

Each of the heat transfer compositions of the invention as defined abovemay additionally comprise a lubricant. In general, the heat transfercomposition comprises a lubricant, in amounts of from about 5 to 50% byweight of the heat transfer composition, preferably about 10 to about50% by weight of the heat transfer composition, preferably from about 20to about 50% by weight of the heat transfer composition, alternativelyabout 20 to about 40% by weight of the heat transfer composition,alternatively about 20 to about 30% by weight of the heat transfercomposition, alternatively about 30 to about 50% by weight of the heattransfer composition, alternatively about 30 to about 40% by weight ofthe heat transfer composition. The heat transfer composition maycomprise a lubricant, in amounts of from about 5 to about 10% by weightof the heat transfer composition, preferably around about 8% by weightof the heat transfer composition.

Commonly used refrigerant lubricants such as polyol esters (POEs),polyalkylene glycols (PAGs), silicone oils, mineral oil, alkylbenzenes(ABs), polyvinyl ethers (PVEs), and poly(alpha-olefin) (PAO) that areused in refrigerationsystems may be used with the refrigerantcompositions of the present invention.

Preferably the lubricants are selected from polyol esters (POEs),polyalkylene glycols (PAGs), mineral oil, alkylbenzenes (ABs) andpolyvinyl ethers (PVE), more preferably from polyol esters (POEs),mineral oil, alkylbenzenes (ABs), and polyvinyl ethers (PVE),particularly from polyol esters (POEs), mineral oil and alkylbenzenes(ABs), most preferably from polyol esters (POEs).

Commercially available mineral oils include Witco LP 250 (registeredtrademark) from Witco, Suniso 3GS from Witco and Calumet R015 fromCalumet. Commercially available alkylbenzene lubricants include Zerol150 (registered trademark) and Zerol 300 (registered trademark) fromShrieve Chemical. Other useful esters include phosphate esters, di-basicacid esters and fluoro esters.

The heat transfer composition of the invention may consist essentiallyof or consist of a refrigerant, including in particular any one ofRefrigerants 1-23, Refrigerants 1 NF-23NF, Refrigerants1GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, a stabilizercomposition and a lubricant as described herein.

A preferred heat transfer composition comprises Refrigerant 1 and from10 to 50% by weight of a polyol ester (POE) lubricant, based on theweight of the heat transfer composition. Polyol ester (POE) lubricantfrom 10 to 50% by weight of the heat transfer composition is sometimesreferred to for convenience as Lubricant 1.

A preferred heat transfer composition comprises Refrigerant 2 andLubricant 1.

A preferred heat transfer composition comprises Refrigerant 3 andLubricant 1.

A preferred heat transfer composition comprises Refrigerant 4 andLubricant 1.

A preferred heat transfer composition comprises Refrigerant 5 andLubricant 1.

A preferred heat transfer composition comprises Refrigerant 6 andLubricant 1

A preferred heat transfer composition comprises Refrigerant 7 andLubricant 1.

A preferred heat transfer composition comprises Refrigerant 8 andLubricant 1.

A preferred heat transfer composition comprises Refrigerant 9 andLubricant 1.

A preferred heat transfer composition comprises Refrigerant 10 andLubricant 1.

A preferred heat transfer composition comprises Refrigerant 11 andLubricant 1.

A preferred heat transfer composition comprises Refrigerant 12 andLubricant 1.

A preferred heat transfer composition comprises Refrigerant 13 andLubricant 1.

A preferred heat transfer composition comprises Refrigerant 14 andLubricant 1.

A preferred heat transfer composition comprises Refrigerant 15 andLubricant 1.

A preferred heat transfer composition comprises Refrigerant 16 andLubricant 1.

A preferred heat transfer composition comprises Refrigerant 17 andLubricant 1.

A preferred heat transfer composition comprises Refrigerant 18 andLubricant 1.

A preferred heat transfer composition comprises Refrigerant 19 andLubricant 1.

A preferred heat transfer composition comprises Refrigerant 20 andLubricant 1.

A preferred heat transfer composition comprises Refrigerant 21 andLubricant 1.

A preferred heat transfer composition comprises Refrigerant 22 andLubricant 1.

A preferred heat transfer composition comprises Refrigerant 23 andLubricant 1.

A preferred heat transfer composition comprises any of Refrigerants1NF-23NF and Lubricant 1.

A preferred heat transfer composition comprises any of Refrigerants1NFGWP150-23NFGWP150 and Lubricant 1.

A preferred heat transfer composition comprises any of Refrigerants1GWP5-12GWP5 and Lubricant 1.

A preferred heat transfer composition comprises any of Refrigerants1NFGWP5-12NFGWP5 and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 1, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 2, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 3, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 4, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 5, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 6, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 7, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 8, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 9, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 10, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 11, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 12, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 13, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 14, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 15, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 16, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 17, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 18, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 19, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 20, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 21, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 22, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 23, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseany of Refrigerants 1NF-23NF, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseany of Refrigerants 1NFGWP150-23NFGWP150, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseany of Refrigerants 1GWP5-12GWP5, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseany of Refrigerants 1NFGWP5-12NFGWP5, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 1, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 2, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 3, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 4, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 5, Stabilizer 1, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 6, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 7, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 8, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 9, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 10, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 11, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 12, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 13, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 14, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 15, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 16, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 17, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 18, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 19, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 20, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 21, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 22, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseRefrigerant 23, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseany of Refrigerants 1NF-23NF, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseany of Refrigerants 1NFGWP150-23NFGWP150, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseany of Refrigerants 1GWP5-12GWP5, Stabilizer 2, and Lubricant 1.

The heat transfer composition of the invention can preferably compriseany of Refrigerants 1NFGWP5-12NFGWP5, Stabilizer 2, and Lubricant 1.

Other additives not mentioned herein can also be included by thoseskilled in the art in view of the teaching contained herein withoutdeparting from the novel and basic features of the present invention.

Combinations of surfactants and solubilizing agents may also be added tothe present compositions to aid oil solubility as disclosed in U.S. Pat.No. 6,516,837, the disclosure of which is incorporated by reference inits entirety.

In addition the refrigerants according to the present invention,including in particular any one of Refrigerants 1-23, Refrigerants 1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, and the heat transfer composition which contain suchrefrigerants, show acceptable toxicity and preferably have anOccupational Exposure Limit (OEL) of greater than about 400.

Heat Transfer Systems, Uses and Methods

The refrigerant (and the heat transfer composition containing therefrigerant) of the invention can be used in heating and coolingapplications.

The compositions disclosed herein are provided for use in heat transferapplications, including, low temperature refrigeration, mediumtemperature refrigeration, vending machines, heat pumps (including heatpump water heaters), dehumidifiers, chillers, and refrigerators andfreezers.

The compositions of the invention may be employed in systems which areused or are suitable for use with R-134a refrigerant, such as existingor new heat transfer systems.

Any reference to the heat transfer composition of the invention refersto each and any of the heat transfer compositions as described herein.Thus, for the following discussion of the uses or applications of theheat transfer compositions of the invention, the heat transfercomposition may comprise or consist essentially of any of therefrigerants described herein, including in particular any one ofRefrigerants 1-23, Refrigerants 1 NF-23NF, Refrigerants1GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, in combination with anyof the stabilizers described herein, including Stabilizer 1 andStabilizer 2, and any of the lubricants discussed herein, includingLubricant 1.

For the purposes of this invention, each and any of the heat transfercompositions as described herein can be used in a heat transfer system,such a low temperature refrigeration system, a medium temperaturerefrigeration system, a vending machine, a heat pump (including a heatpump water heater), dehumidifiers, a chiller, and a refrigerator and/orfreezer. The heat transfer system according to the present invention cancomprise a compressor, an evaporator, a condenser and an expansiondevice, in communication with each other.

Examples of commonly used compressors, for the purposes of thisinvention include reciprocating, rotary (including rolling piston androtary vane), scroll, screw, and centrifugal compressors. Thus, thepresent invention provides each and any of the refrigerants and/or heattransfer compositions as described herein for use in a heat transfersystem comprising a reciprocating, rotary (including rolling piston androtary vane), scroll, screw, or centrifugal compressor.

Examples of commonly used expansion devices, for the purposes of thisinvention include a capillary tube, a fixed orifice, a thermal expansionvalve, and an electronic expansion valve. Thus, the present inventionprovides each and any of the refrigerants and/or heat transfercompositions as described herein for use in a heat transfer systemcomprising a capillary tube, a fixed orifice, a thermal expansion valve,or an electronic expansion valve.

For the purposes of this invention, the evaporator and the condensertogether form a heat exchanger, preferably selected from a finned tubeheat exchanger, a microchannel heat exchanger, a shell and tube, a plateheat exchanger, and a tube-in-tube heat exchanger. Thus, the presentinvention provides each and any of the refrigerants and/or heat transfercompositions as described herein for use in a heat transfer systemwherein the evaporator and condenser together form a finned tube heatexchanger, a microchannel heat exchanger, a shell and tube, a plate heatexchanger, or a tube-in-tube heat exchanger.

The present invention also provides heat transfer systems and methodswhich utilize sequestration materials to help reduce the negative impactthat refrigerant and/or lubricant deterioration may have on systemoperation. With respected to sequestration materials, the systems of thepresent invention preferably include a sequestration material in contactwith at least a portion of a refrigerant according to the presentinvention wherein the temperature of the sequestration material and/orthe temperature of the refrigerant when in said contact are at atemperature that is preferably at least about 10° C.

For the purposes of the systems and methods of the invention asdescribed in this application, the term “about” in relation totemperatures means that the stated temperature can vary by an amount of+/−5° C. It will be understood that for temperatures described as being“about” an indicated value, the present invention included embodimentsin which the temperature is the stated temperature +/−2° C., and morepreferably +/−1° C., most preferably +/−0.5° C.

Any and all of the refrigerants and any and all of the sequestrationmaterials as described herein can be used in the systems of the presentinvention. In preferred embodiments, the systems of the presentinvention include a sequestration material in contact with at least aportion of a refrigerant according to the present invention, includingin particular any one of Refrigerants 1-23, Refrigerants 1NF-23NF,Refrigerants 1GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150,Refrigerants 1GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5.Preferably the sequestration material comprises: (a) an anion exchangeresin, (b) activated alumina adsorbants, (c) a moisture-removingmolecular sieve, (d) a molecular sieve (preferably a zeolite) comprisingcopper, silver, lead or a combination thereof, and (e) a combination ofabove materials.

Examples of anion exchange resins that are commercially available anduseful according to the present invention include Amberlyst A21,Amberlyst A22, and Dowex Marathon.

Examples of activated alumina that are commercially available and usefulaccording to the present invention include F200 sold by BASF and CLR-204sold by Honeywell.

Examples of moisture-removing molecular sieves that are commerciallyavailable and useful according to the present invention include sodiumaluminosilicate molecular sieves have pore size types 3 A, 4 A, 5 A, and13X.

An example of a zeolite molecular sieve that is commercially availableis IONSIV D7310-C with activated sites used to remove specificdecomposition products.

As used in connection with the sequestration material, the term “incontact with at least a portion” is intended in its broad sense toinclude each of the sequestration materials and any combination ofsequestration materials being in contact with the same or separateportions of the refrigerant in the system and is intended to include butnot necessarily limited to embodiments in which each type or specificsequestration material is: (i) located physically together with eachother type or specific material, if present; (ii) is located physicallyseparate from each other type or specific material, if present, and(iii) combinations in which two or more materials are physicallytogether and at least one sequestration material is physically separatefrom at least one other sequestration material.

The amount that the anion exchange resin is preferably present in systemin an amount of from about 5% to about 60% by weight based on the totalof amount of lubricant and anion exchange resin present in the system.Preferably, the anion exchange resin is present in an amount of of fromabout 20% to about 50% by weight and most preferably in an amount offrom about 20% to 30% by weight based on the total of amount oflubricant and anion exchange resin present in the system.

The amount of anion exchange resin described herein refers to the dryweight of the anion exchange resin.

The amount that the zeolite molecular sieve that is preferably presentthe system is from about 1% to about 30% by weight based on the total ofamount of lubricant and zeolite molecular sieve present in the system.Preferably, the zeolite molecular sieve is preferably present in anamount of from about 10% to about 30% by weight based on the total ofamount of lubricant and zeolite molecular sieve present in the system.

The moisture-removing the molecular sieve (e.g., sodium about 60% byweight relative to the amount of lubricant present and moisture-removingmaterial in the system. Preferably, the molecular sieve may be presentin an amount of 30% to 45% by weight based on the total of amount oflubricant and moisture-removing molecular sieve present in the system.

The amount that the activated alumina that is preferably present insystem is from about 5% to about 60% by weight based on the total ofamount of lubricant and activated alumina present in the system.

Cascaded Refrigeration

The present invention provides heat transfer systems, uses and methodsthat include cascaded refrigeration systems, with such system containingany of the refrigerants disclosed herein, including in particular anyone of Refrigerants 1-23, Refrigerants 1NF-23NF, Refrigerants1GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, and any heat transfercomposition as disclosed herein. Any of the equipment described hereingenerally with respect to use in heat transfer systems is adapatable foruse in any of the cascade systems as described herein.

A cascade system typically has at least two stages, which are usuallyreferred to as the “high stage” and the “low stage”. A generalized flowdiagram for a cascade heat transfer system is provided in FIG. 4 hereof.The heat transfer compositions of the invention are particularlyprovided for the high stage of the cascade system. In a cascade system,the high stage cycle generally has an air-to-refrigerant condenser and arefrigerant-to-refrigerant evaporator. The high stage typically has apositive displacement compressor which may be a reciprocating or rotarycompressor, and a thermal or electronic expansion valve. The refrigerantevaporating temperature of the high stage is preferably in the range ofabout −10 to about 20° C. The condensing temperature of the high stageis preferably in the range of about 40 to about 70° C.

The low stage of the preferred cascade system generally (indentified asInter. HX in FIG. 4) has a refrigerant-to-refrigerant condenser and arefrigerant-to-air evaporator to cool the product. The low stagetypically has a positive displacement compressor which may be areciprocating or rotary compressor, and a thermal or electronicexpansion valve. The refrigerant evaporating temperature of the lowstage is preferably in the range of about −40 to about −10° C. Thecondensing temperature of the low stage is preferably in the range ofabout 0 to about 30° C. The low stage refrigerant may be, for example,carbon dioxide.

The present invention thus includes cascaded systems and methods inwhich any of the refrigerants described herein, including in particularany one of Refrigerants 1-23, Refrigerants 1NF-23NF, Refrigerants1GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, is used as areplacement for or a retrofit for R-134a in cascade refrigerationsystem.

For the purpose of illustration, two cascade systems of knowconfiguration are illustrated herein in FIG. 1A and FIG. 1B, and eachcascade system of this type, and all know variations of such systems,are improved by the use of any one of the refrigerants of the presentinvention, including in particular any one of Refrigerants 1-23,Refrigerants 1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, and any of the heat transfer compositions whichinclude any one of such refrigerants. For the purposes of convenience,such cascade systems are referred to herein as Cascade System 1A andCascade System 1B, respectively, and each is described in detail below,

Cascade System 1A

One example of a cascade system of a general type that has used R-134ais illustrated in FIG. 1A hereof as system 100, which is a refrigerationsystem of the type commonly used for commercial refrigeration insupermarkets. The system 100 is a direct expansion system which providesboth medium and low temperature refrigeration via medium temperaturerefrigeration circuit 110 and low temperature refrigeration circuit 120.Medium temperature refrigeration is typically provided at an evaporationtemperature level of about −10° C.

The level and type of cascade refrigeration disclosed herein inconnection with Cascade System 1A is commonly used for products such asdairy, deli and fresh food. The individual temperature level for thedifferent products is adjusted based on the product requirements. Lowtemperature refrigeration is typically provided at an evaporationtemperature level of about −25° C. This level of refrigeration iscommonly used for products such as ice cream and frozen goods. Again,the individual temperature level for the different products is adjustedbased on the product requirements. In preferred embodiments, the lowsystem evaporation temperatures is −25° C., +/−3° C. or +/−2° C. In suchsystems a medium temperature refrigeration circuit 110 has or would bedesigned to have, or would be useful with R134a as its refrigerant, andaccording to preferred embodiments of the present invention any of therefrigerants and/or heat transfer compositions are used in such a systemin place of, or a replacement for, or as a retrofit for R-134a. Such acascade refrigeration system of the general type illustrated in FIG. 1Ais referred to herein for convenience as Cascade System 1A.

In Cascade System 1A the medium temperature refrigeration circuit 110preferably provides both the medium temperature cooling and removes therejected heat from the lower temperature refrigeration circuit 120 via aheat exchanger 130. The medium temperature refrigeration circuit 110extends between, for example, a roof 140, a machine room 141 and a salesfloor 142. The low temperature refrigeration circuit 120 on the otherhand has an alternative refrigerant, for example R744, as itsrefrigerant. The low temperature refrigeration circuit 120 extendsbetween the machine room 141 and the sales floor 142. Usefully, asdiscussed above, R744 has a low GWP.

Since prior systems according to Cascade System 1A have been designedfor use with and have been used with R134a as the second refrigerant(i.e., in the medium temperature circuit), the present inventionincludes using any of the refrigerants as disclsclosed herein, includingin particular any one of Refrigerants 1-23, Refrigerants 1 NF-23NF,Refrigerants 1 GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150,Refrigerants 1 GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5, as thesecond refrigerant.

Cascade System 1B

FIG. 1B shows an example of a cascade refrigeration system 100comprising a medium temperature refrigeration circuit 110 and a lowtemperature refrigeration circuit 120. To the extent systems of the typedescribed in Cascade System 1A have elements and features in common withCascade System 1B, the description of those elements or features inconnection with Cascade System 1A applies to Cascade System 1B.

The low temperature refrigeration circuit 120 as illustrated in FIG. 1Bhas a compressor 121, an interface with a heat exchanger 130 forrejecting heat to ambient conditions, an expansion valve 122 and anevaporator 123. The low temperature refrigeration circuit 120 interfaceswith the medium temperature refrigeration circuit 110 through theinter-circuit heat exchanger 150, which serves to reject heat to fromthe low temperature refrigerant to the medium temperature refrigerant,which may be any refrigerant according to the present invention,including in particular any one of Refrigerants 1-23, Refrigerants 1NF-23NF, Refrigerants 1 GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants 1 GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, and thereby produce a subcooled refrigerant liquid inthe low temperature refrigerant cycle. The evaporator 123 is interfacedwith a space to be chilled, such as the inside of a freezer compartment.The components of the low temperature refrigeration circuit areconnected in the order: evaporator 123, compressor 121, heat exchanger130, inter-circuit heat exchanger 150, and expansion valve 122. Thecomponents are connected together via pipes 124 filled with a lowtemperature refrigerant.

Since prior systems according to Cascade System 1B have been designedfor use with and used with R134a as the second refrigerant (i.e., in themedium temperature circuit), the present invention includes using any ofthe refrigerants as disclsclosed herein, including in particular any oneof Refrigerants 1-23, Refrigerants 1 NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5, as the secondrefrigerant.

The operation of each of Cascade System 1A and 1B will be described inmore detail, especially with respect to features and elements that applyto each system, and in this connection features and elements that aresimilar in each system are labelled in each figure with the samenumeral. The system 100 can in preferred embodiments span multipleareas, for example, the following three areas of a building: a roofwhere the condensers 113 and 130 are located; a machine room where thecompressors 111, 112, heat exchanger 150, receiving tank 114 andexpansion device 118 are located; and a sales floor 142 where the LTcase, the MT case, and each of their expansion devices are located.

The low temperature refrigeration circuit 120 and the medium temperaturerefrigeration circuit thus each extend between the sales floor, themachine room and the roof. In use, the medium temperature circuit 110provides medium temperature chilling to spaces to be chilled via theevaporator 119 and the low temperature circuit 120 provides lowtemperature chilling to spaces to be chilled via the evaporator 123. Themedium temperature circuit 110 also removes heat from the liquidcondensate from the low temperature condenser 120, thus providingsubcooling to the liquid entering the evaporator 123.

The individual and overall functionality of the various components ofthe medium temperature refrigeration circuit 110 will now be described.Starting with heat exchanger 150, as described above the mediumtemperature refrigerant absorbs heat from the low temperaturerefrigerant via the heat exchanger 150. This absorption of heat causesthe refrigerant in the medium temperature circuit 150, which is a lowtemperature gas and/or a mixture of gas and liquid on entering the heatexchanger 150, to be change liquid to the gas phase and/or to increasethe temperature of the gas in the case where superheating will beproduced. On leaving the heat exchanger 150, the gaseous refrigerant issucked into the compressor 111 (along with the refrigerant from theevaporator 119) and is compressed by the compressor 111 to a hightemperature and high pressure gas. This gas is released into the pipes115 and travels to the condenser 113 which, in this example, is arrangedon a roof of a building. In the condenser 113, the gaseous mediumtemperature refrigerant releases heat to the outside ambient air and sois cooled and condenses to a liquid. After the condenser 113, the liquidrefrigerant collects in a fluid receiver 114. In this example, the fluidreceiver 114 is a tank. On leaving the fluid receiver 114, the liquidrefrigerant is manifolded to parallel connected medium temperaturebranch 116 and subcooling cooling branch 117. In the medium temperaturebranch 116, the liquid refrigerant flows to the expansion valve 112which is used to lower the pressure and therefore temperature of theliquid refrigerant. The relatively cold liquid refrigerant then entersthe heat exchanger 119 where it absorbs heat from the space to bechilled which is interfaced with the evaporator 119 f. In the subcoolingbranch 117, the liquid refrigerant similarly flows first to an expansionvalve 118 where the pressure and temperature of the refrigerant islowered. After the valve 118, the refrigerant flows to the inter-circuitheat exchanger 150, as described above. From there, the gaseousrefrigerant from the heat exchanger is sucked by the compressor 111 tothe compressor 111 where it re-joins the refrigerant from the mediumtemperature cooling branch 116.

Although not mentioned above, it will be clear that to function asintended, the temperature of the refrigerant in the medium temperaturecircuit 110 as it enters the heat exchanger 150 must be less than thetemperature of the refrigerant in the low temperature circuit 120 as itenters the heat exchanger 150. If this were not the case, the mediumtemperature circuit 110 would not provide the desired subcooling to thelow temperature refrigerant in circuit 120.

Cascade Systems 2 and 3

In addition to use of the present refrigerants as replacements forR-134a in known R-134a systems, applicants have developed inventivecascade refrigerations systems and and each of the refrigerantsdescribed herein, including in particular any one of Refrigerants 1-23,Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants 1 GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, can be used in these inventive systems, and inparticular as the refrigerant in the higher temperature stage circuit.These two embodiments are illustrated in FIGS. 2 and 3 herein and areexplained in detail below.

The cascade system according to preferred embodiments preferablycomprises: one or more first refrigeration units, each refrigerationunit containing a first refrigeration circuit, each first refrigerationcircuit comprising an evaporator and a heat exchanger; and a secondrefrigeration circuit; wherein each heat exchanger is arranged totransfer heat energy between its respective first refrigeration circuitand the second refrigeration circuit. The second circuit may be locatedsubstantially completely outside of said plurality of firstrefrigeration units. As used herein, the term “substantially completelyoutside of said plurality of first refrigeration units” means that thecomponents of the second refrigeration circuit are not within said firstrefrigeration units except that transport piping and the like which maybe considered part of the second refrigeration circuit can pass into thefirst refrigeration units in order to provide heat exchange between therefrigerant of the first and second refrigeration circuits. As usedherein, the term “first refrigeration unit” means an at least partiallyclosed or closable structure that is capable of providing cooling withinat least a portion of that structure and which is structurally distinctfrom any structure enclosing or containing said second refrigerationcircuit in its entirety. According to and consistent with such meanings,the first refrigeration circuits of the present invention are sometimesreferred to herein as “self-contained” when contained within such firstrefrigeration units, in accordance with the meanings described herein.

Each refrigeration unit may be arranged within a first area. The firstarea may be a shop floor. This means that each first refrigerationcircuit may also be located within a first area, such as a shop floor.

Each refrigeration unit may comprise a space and/or objects containedwithin a space to be chilled, and preferably that space is within therefrigeration unit. Each evaporator may be arranged to chill itsrespective space/objects, preferably by cooling air within the space tobe chilled.

As mentioned above, the second refrigeration circuit may have componentsthereof that extend between the first refrigeration unit and a secondarea. The second area may be, for example, a machine room which houses asubstantial portion of the components of the second refrigerationcircuit.

The second refrigeration circuit may extend to a second and a thirdarea. For The third area may be an area outside of the building orbuildings in which the first refrigeration units and the second area(s)are located. This allows for ambient cooling to be exploited.

Each first refrigeration circuit may comprise at least one fluidexpansion device. The at least one fluid expansion device may be acapillary tube or an orifice tube. This is enabled by the conditionsimposed on each first refrigeration circuit by its respectiverefrigeration unit being relatively constant. This means that simplerflow control devices, such as capillary and orifice tubes, can be andpreferably are used to advantage in the first refrigeration circuits.

The average temperature of each of the first refrigeration circuits maybe lower than the average temperature of the second refrigerationcircuit. This is because the second refrigeration circuit may be used toprovide cooling, that is, remove heat from, the first refrigerationcircuits; and each first refrigeration circuit may cool a space to bechilled in its respective refrigeration unit.

The second refrigeration circuit may cool, that is, remove heat from,each of the first refrigeration circuits.

Each heat exchanger may be arranged to transfer heat energy between itsrespective first refrigeration circuit and the second refrigerationcircuit at a respective circuit interface location.

Each of the circuit interface locations may be coupled inseries-parallel combination with each other of the circuit interfacelocations. Usefully, this means that if one of the circuit interfacelocations, first refrigeration circuits, or first refrigeration unitshas a fault or blockage detected, the location, circuit or unit at faultcan be isolated and/or bypassed by the second refrigeration circuit sothat faults do not propagate through the system.

Each of the circuit interface locations may be coupled in series with atleast one other circuit interface location.

Each of the circuit interface locations may be coupled in series witheach other of the circuit interface locations.

Each of the circuit interface locations may be coupled in parallel withat least one other circuit interface location.

Each of the circuit interface locations may be coupled in parallel witheach other of the circuit interface locations.

In each preferred embodiment disclosed herein, the second refrigerant isany refrigerant, including as described herein and/or any heat transfercomposition as described herein, in particular any one of Refrigerants1-23, Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150,Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1 GWP5-12GWP5, andRefrigerants 1 NFGWP5-12NFGWP5. Since the preferred refrigerants of thepresent invention are both low GWP and non-flammable, the use of them issuch systems is highly advantageous since the second refrigerant circuitmay span numerous areas, and so having a non-flammable refrigerant isimportant for reducing the severity of potential leaks.

The second refrigeration circuit may comprise a second evaporator. Thesecond evaporator may be coupled in parallel with the circuit interfacelocations.

The first refrigerant, which is used in the first refrigerant circuits,may comprise any of R744, hydrocarbons, R1234yf, R1234ze(E), R455A andcombinations of these. Hydrocarbons may comprise any of R290, R600a orR1270. These refrigerants are low GWP.

The first refrigerant may be one of R744, hydrocarbons, R1234yf,R1234ze(E), R455A and combinations of these.

The system as illustrated in each of FIGS. 2 and 3 has a number ofrefrigeration units and each of the refrigeration units has at least onededicated refrigeration circuit arranged within it. That is, eachrefrigeration unit contains at least one refrigeration circuit.

The refrigeration circuit contained within a refrigeration unit maycomprise at least a heat exchanger that removes heat to the refrigerantin the circuit, and an evaporator that adds heat to the refrigerant.

The refrigeration circuit contained within a refrigeration unit maycomprise a compressor, at least a heat exchanger that removes heat fromthe refrigerant in the circuit (preferably by removing heat from therefrigerant vapor exiting the compressor), and an evaporator that addsheat to the refrigerant (preferably by cooling the area of therefrigeration unit being chilled). Although it is contemplated that thesize of the compressor used in the first refrigeration circuit, ingenerally the compressor may be a small size compressor. As used herein,the term “small size compressor” means the compressor has a power ratingof not greater than about 1 horsepower. The compressor size may be from0.1 horsepower to about 1 horsepower. The compressor size may be from0.1 horsepower to about 0.75 horsepower. The compressor size may be from0.1 horsepower to about 0.5 horsepower.

A refrigeration unit may be an integrated physical entity, i.e. anentity which is not designed to be dismantled into component parts. Arefrigeration unit might be a fridge or a freezer, for example.

The refrigeration circuits provided within each refrigeration unit maythemselves be cooled by a common refrigeration circuit at leastpartially external to the refrigeration units. In contrast to thededicated refrigeration circuits contained within each refrigerationunit, common refrigeration circuits (which are generally referred toherein as second and third refrigeration circuits) may be extendedcircuits which extend between multiple areas of the building housing theunits: such as between a sales floor (where the refrigeration units arearranged) and a machine room and/or a roof or outside area. Eachrefrigeration unit may comprise at least one compartment for storinggoods, such as perishable goods. The compartments may define a space tobe chilled by a refrigeration circuit contained within the refrigerationunit.

Any one of the refrigerants described herein, including in particularRefrigerants 1-23, Refrigerants 1 NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5, may be used as therefrigerant in the second refrigeration circuits in any one of thecascade refrigeration systems described herein, including each ofCascade Systems 2 and 3, as described herein.

Cascade System 2

A cascade refrigeration system useful with the refrigerants of thepresent invention is described below in connection with FIG. 2. For thepurposes of convenience such cascade refrigeration systems are referredto herein as Cascade System 2, and of the refrigerants as disclosedherein, including in particular Refrigerants 1-23, Refrigerants1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, may be used in any Cascade System 2 as the refrigerantin the second refrigeration circuit (i.e., in the medium temperaturerefrigeration circuit).

FIG. 2 shows a refrigeration system 200 which has, for example, threefirst refrigeration circuits 220 a, 220 b, 220 c. Each of the firstrefrigeration circuits 220 a, 220 b, 220 c has an evaporator 223, acompressor 221, a heat exchanger 230 and an expansion valve 222. In eachcircuit 220 a, 220 b, 220 c, the evaporator 223, the compressor 221, theheat exchanger 230 and the expansion valve 222 are connected in serieswith one another in the order listed. Each of the first refrigerationcircuits 220 a, 220 b, 220 c is included within a separate respectiverefrigeration unit (not shown). In this example, each of the threeillustrated refrigeration units is a freezer unit and the freezer unithouses its respective first refrigeration circuit. In this way, eachrefrigeration unit comprises a self-contained and dedicatedrefrigeration circuit.

The refrigeration units (not shown), and therefore the firstrefrigeration circuits 220 a, 220 b, 220 c, are arranged on a salesfloor 242 of a supermarket.

In this example, the refrigerant in each of the first refrigerationcircuits 220 a, 220 b, 220 c is a low GWP refrigerant such as R744,hydrocarbons (R290, R600a, R1270), R1234yf, R1234ze(E) or R455A. As theskilled person will appreciate, the refrigerants in each of the firstrefrigeration circuits 220 a, 220 b, 220 c may the same or different tothe refrigerants in each other of the first refrigeration circuits 220a, 220 b, 220 c.

The refrigeration system 200 also has a second refrigeration circuit210. The second refrigeration circuit 210 has a compressor 211, acondenser 213 and a fluid receiver 214. The compressor 211, thecondenser 213 and the fluid receiver 214 are connected in series and inthe order given. The second refrigeration circuit 210 also has fourparallel connected branches: three medium temperature cooling branches217 a, 217 b, 217 c; and one low temperature cooling branch 216. Thefour parallel connected branches 217 a, 217 b, 217 c and 216 areconnected between the fluid receiver 214 and the compressor 211. Each ofthe medium temperature cooling branches 217 a, 217 b, 217 c has anexpansion valve 218 and an evaporator 219, 219 b and 219 c,respectively. The expansion valve 218 and evaporator 219 are connectedin series and in the order given between the fluid receiver 214 and thecondenser 211. The low temperature cooling branch 216 has an expansionvalve 212 and an interface, in the form of inlet and outlet piping,conduits, valves and the like (represented collectively as 260 a, 260 band 260 c, respectively) which bring the second refrigerant to and fromeach of the heat exchangers 230 a, 230 b, 230 c of the firstrefrigeration circuits 220 a, 220 b, 220 c. The low temperature coolingbranch 216 interfaces each of the heat exchangers 230 a, 230 b, 230 c ofthe first refrigeration circuits 220 a, 220 b, 220 c at a respectivecircuit interface location 231 a, 231 b, 231 c. Each circuit interfacelocation 231 a, 231 b, 231 c is arranged in series-parallel combinationwith each other of the circuit interface locations 231 a, 231 b, 231 c.

The medium temperature refrigeration circuit 210 has components whichextend between the sales floor 242, a machine room 241 and a roof 140.The low temperature cooling branch 216 and the medium temperaturecooling branches 217 a, 217 b, 217 c of the medium temperaturerefrigeration circuit 210 are located on the sales floor 242.

The compressor 211 and the fluid receiver 214 are located in the machineroom 241.

The condenser 213 is located where it can be readily exposed to ambientconditions, such as on the roof 240.

In use:

-   -   each of the first refrigeration circuits 220 a, 220 b, 220 c        absorbs heat via their evaporators 223 to provide low        temperature cooling to a space to be chilled (not shown);    -   the second refrigeration circuit 210 absorbs heat from each of        the heat exchangers 230 a, 230 b, 230 c to cool the first        refrigeration circuits 220 a, 220 b, 220 c;    -   the second refrigeration circuit 210 absorbs heat at each of the        evaporators 219 to provide medium temperature cooling to spaces        to be chilled (not shown); and    -   the refrigerant in the second refrigeration circuit 210 is        chilled in the chiller 213.

A number of beneficial results can be achieved using the arrangementshown in FIG. 2, particularly from each first refrigeration circuit 230being self-contained in a respective refrigeration unit.

For example, installation and uninstallation of the refrigeration unitsand the overall cascaded refrigeration system 200 is simplified. This isbecause the refrigeration units, with their built-in, self-containedfirst refrigeration circuits 220 a, 220 b, 220 c, can be easilyconnected or disconnected with the second refrigeration circuit 210,with no modification to the first refrigeration circuit 220, 220 b, 220c required. In other words, the refrigeration units may simply be‘plugged’ in to, or out of, the second refrigeration circuit 210.

Another advantage is that each refrigeration unit, including itsrespective first refrigeration circuit 220 a, 220 b, 220 c, can befactory tested for defaults before being installed into a liverefrigeration system 200. This mitigates the likelihood of faults, whichcan include leaks of potentially harmful refrigerants. Accordingly,reduced leak rate can be achieved.

Another advantage is that the lengths of the first refrigerationcircuits 220 a, 220 b, 220 c can be reduced since each circuit 220 a,220 b, 220 c is arranged in its respective refrigeration unit, and doesnot extend between a series of units. The reduced circuit length canresult in improved efficiency as there is reduced heat infiltration inshorter lines due to reduced surface area. Further, reduced circuitlength can also result in reduced pressure drop, which improves thesystem 200 efficiency.

The reduced circuit length, and the provision of the circuitsself-contained within respective refrigeration units, also provides theability to use more flammable refrigerants, such as R744, Hydrocarbons(R290, R600a, R1270), R1234yf, R1234ze(E) or R455A, in the first (lowtemperature) circuit which applicants have come to appreciate is ahighly beneficial result. This is because both the likelihood of therefrigerant leaking is reduced (as discussed above) and because, even ifthe refrigerant were to leak, the leak would be contained to therelatively small area and containable area of the respectiverefrigeration unit, and because of the small size of the units, only arelatively small amount of refrigerant charge is used. In addition, thisarrangement would permit the use of relatively low cost flame mitigationcontingency procedures and/or devices since the area containingpotentially flammable materials is much smaller, confined and uniform.Such more flammable refrigerants can have lower global warming potential(GWP). Advantageously therefore, governmental and societal targets forthe use of low GWP refrigerants may be met and potentially even exceededwithout compromising on safety of the system.

Another advantage is that each first refrigeration circuit 220 a, 220 b,220 c may only cool their respective refrigeration unit. This means thatthe load on each first refrigeration circuit 220 a, 220 b, 220 c mayremain relatively constant. That is, constant conditions are applied tothe condensing 231 and evaporating 223 stages of the first refrigerationcircuit 220. This allows for the simplification of the design of thefirst refrigeration circuit 220 in that passive expansion devices 222,such as capillary tubes or orifice tubes, can be used. This is incontrast to more complex circuits where electronic expansion devices andthermostatic expansion valves need to be used. Since the use of suchcomplex devices is avoided, costs can be reduced and reliability can beincreased.

Furthermore, importantly, the provision of a flooded heat exchanger inthe second refrigeration circuit according to such embodiments resultsin improved heat transfer between the first and second circuits.Accordingly, the efficiency of the overall refrigeration system isimproved.

There are several advantages that may arise from circuit interfacelocations being coupled in parallel with other circuit interfacelocations. One advantage may be that resilience is provided in thesystem since a fault associated with or suffered at one circuitinterface location will not impact other circuit interface locations.This is because each circuit interface location is serviced by arespective branch of the second refrigeration circuit. Another advantagemay be that heat transfer efficiency between first and secondrefrigeration circuits is improved because the temperature of the secondrefrigerant before each circuit interface location can be keptrelatively constant. In contrast, if two circuit interface locationswere coupled in series, the temperature of the refrigerant in the secondrefrigeration circuit may be higher before the downstream circuitinterface location, than before the upstream circuit interface location.

Overall, the provision of a plurality of first refrigeration circuitsaccording to the present invention, with each one arranged in arespective refrigeration unit, preferably being arranged as aself-contained refrigeration circuit, has such benefits as: reducingleak rates; simplifying the overall refrigeration system; enabling theuse of otherwise unsafe low GWP refrigerants; improving maintenance andinstallation; and reducing pressure drop, leading to improved systemefficiency.

As the person skilled in the art will appreciate, there may be anynumber of first refrigeration circuits 220. In particular, there may beas many first refrigeration circuits 220 as there are refrigerationunits to be cooled. Accordingly, the second refrigeration circuit 210may be interfaced with any number of first refrigeration circuits 220.

As will be clear to the skilled person, there may be any number andarrangement of medium temperature cooling branches 217 and evaporators218.

Cascade System 3

In alternative arrangements, each first refrigeration circuit 220 may bearranged fully in parallel with each other first refrigeration circuit220. An example of such an arrangement is shown in FIG. 3 as is referredto herein for convenience as Cascade System 3. FIG. 3 shows a system 300where each circuit interface location 231 a, 231 b, 231 c is arrangedfully in parallel with each other circuit interface location 231 a, 231b, 231 c. The components of the system 300 are otherwise the same as insystem 200 (described in reference to FIG. 2), and components of thesystem 300 function in substantially the same way as the system 200,although it will be appreciated that the performance of the overallsystem and other important features of the overall system can besignificantly impacted by this change in the arrangement.

Usefully, this means that a given portion of refrigerant from the secondrefrigeration circuit 210, which can be any refrigerant as disclosedherein, including in particular Refrigerants 1-23, Refrigerants 1NF-23NF, Refrigerants 1 GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants 1 GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, only passes through one heat exchanger 230 before it isreturned to the compressor 211. This arrangement thus ensures that eachof the heat exchangers 230 will receive second refrigerant at about thesame temperature, since the arrangement prevents any of the heatexchanger from receiving a portion of the refrigerant that is pre-warmedas a result of passing through an upstream heat exchanger, as would bethe case in a series arrangement;

As will be clear to the person skilled in the art, many otherarrangements of the circuit interface locations 231 a, 231 b, 231 c withrespect to one and the second refrigeration circuit 210 can be achievedand indeed are envisaged.

An example of a further possible alteration of any of the systemsforming part of this disclosure, including in particular any of CascadeSystems 1A, 1B, 2 and 3, is that any number of the self-containedrefrigeration circuits may include a suction line heat exchanger (SLHX).

Heat Transfer Methods

The refrigerants, including in particular Refrigerants 1-23,Refrigerants 1 NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, and any heat transfer composition of the presentinvention containing any such refrigerant, can be used in a method ofcooling comprising condensing a heat transfer composition andsubsequently evaporating said composition in the vicinity of an articleor body to be cooled.

Thus, the invention relates to a method of cooling in a heat transfersystem comprising an evaporator, a condenser and a compressor, theprocess comprising i) condensing a refrigerant or heat transfercomposition as described herein; and ii) evaporating the refrigerant inthe vicinity of body or article to be cooled; wherein the evaporatortemperature of the heat transfer system is in the range of from about−40° C. to about +10° C.

Alternatively, or in addition, the heat transfer composition can be usedin a method of heating comprising condensing the heat transfercomposition in the vicinity of an article or body to be heated andsubsequently evaporating said composition.

Thus, the invention relates to a method of heating in a heat transfersystem comprising an evaporator, a condenser and a compressor, theprocess comprising i) condensing a refrigererant or heat transfercomposition as described herein, in the vicinity of a body or article tobe heated and

ii) evaporating the refrigerant wherein the evaporator temperature ofthe heat transfer system is in the range of about −30° C. to about 5° C.

Thus, any of the refrigerant and heat transfer compositions describedherein can be used in any one of:

-   -   low temperature refrigeration systems;    -   medium temperature refrigeration systems;    -   vending machines;    -   heat pumps, including heat pump water heater;    -   dehumidifiers,    -   chillers, particularly a positive displacement chillers, more        particularly an air cooled or water cooled direct expansion        chiller (preferably water cooled), which is either modular or        conventionally singularly packaged,    -   domestic refrigerators,    -   domestic freezers,    -   industrial freezers,    -   industrial refrigerators,    -   water cooler.

The term “refrigeration system” refers to any system or apparatus or anypart or portion of such a system or apparatus which employs arefrigerant to provide cooling.

The heat transfer composition of the invention is provided for use inmobile air conditioning applications and in commercial and industrialstationary air conditioning applications, particularly in chillers thatcool water to provide air conditioning in commercial and industrialapplications. Thus, any of the heat transfer compositions describedherein can be used in any one of:

-   -   mobile air conditioning, particularly air conditioning in        trucks, buses and trains,    -   chiller applications, particularly a positive displacement        chiller or a centrifugal chiller used to cool water to provide        industrial and/or commercial air conditioning.

The heat transfer compositions of the invention are Iso provided for usein heat pump applications. Thus, any of the heat transfer compositionsdescribed herein can be used in any one of:

-   -   a residential heat pump, such as a residential air to water heat        pump/hydronic system, water heater heat pumps,    -   dehumidifier,    -   an industrial heat pump system, or a commercial heat pump        system.

In particular, R-134a used any of the above-listed systems and equipmentand/or the below-described systems and equipment may be retrofitted orreplaced with the inventive refrigerants and heat transfer compositionsof the present invention.

Each of the heat transfer compositions described herein is particularlyprovided for use in a low temperature refrigeration system (with anevaporator temperature in the range of about −40 to about −12° C.,particularly about −32° C.).

Each of the heat transfer compositions described herein is particularlyprovided for use in a medium temperature refrigeration system (with anevaporator temperature in the range of about −12 to about 0° C.,particularly about 70° C.).

Each of the heat transfer compositions described herein is particularlyprovided for use in a cascade refrigeration system (having a high stagerefrigerant and a low stage refrigerant). The heat transfer compositionsof the invitation are used as the high stage refrigerant in the cascadesystem (which generally has an evaporator temperature in the range ofabout −20 to about 10° C., particularly about −7° C.).

The heat transfer composition of the invention is provided for use in aresidential heat pump system, wherein the residential heat pump systemis used to supply warm air (said air having a temperature of forexample, about 18° C. to about 24° C., particularly about 21° C.) tobuildings in the winter. It is usually the same system as theresidential air-conditioning system, while in the heat pump mode therefrigerant flow is reversed and the indoor coil becomes the condenserand the outdoor coil becomes the evaporator. Typical system types aresplit and mini-split heat pump system. The evaporator and condenser areusually a round tube plate fin or microchannel heat exchanger. Thecompressor is usually a reciprocating or rotary (rolling-piston orscroll) compressor. The expansion valve is usually a thermal orelectronic expansion valve. The refrigerant evaporating temperature ispreferably in the range of about −20 to about 3° C. The condensingtemperature is preferably in the range of about 35 to about 50° C.

The heat transfer composition of the invention is provided for use in aresidential air-to-water heat pump hydronic system, wherein theresidential air-to-water heat pump hydronic system is used to supply hotwater (said water having a temperature of for example about 50° C.) tobuildings for floor heating or similar applications in the winter. Thehydronic system usually has a round tube plate fin or microchannelevaporator to exchange heat with ambient air, a reciprocating or rotarycompressor, a plate condenser to heat the water, and a thermal orelectronic expansion valve. The refrigerant evaporating temperature ispreferably in the range of about −20 to about 3° C. The condensingtemperature is preferably in the range of about 50 to about 90° C.

The heat transfer composition of the invention is provided for use in acommercial air-conditioning system wherein the commercial airconditioning system can be a chiller which is used to supply a chilledheat transfer fluid such as water (said heat transfer fluid, e.g. water,having a temperature of for example about 7° C.) to large buildings suchas offices and hospitals, etc. Depending on the application, the chillersystem may be running all year long. The chiller system may beair-cooled or water-cooled. The air-cooled chiller usually has a plateor shell-and-tube evaporator to supply chilled water, a centrifugalcompressor or a positive displacement compressor which may be areciprocating or scroll compressor, a round tube plate fin ormicrochannel condenser to exchange heat with ambient air, and a thermalor electronic expansion valve. The water-cooled system usually has ashell-and-tube evaporator to supply chilled water, a centrifugalcompressor or a positive displacement compressor which may be areciprocating or scroll compressor, a shell-and-tube condenser toexchange heat with water from cooling tower or lake, sea and othernatural recourses, and a thermal or electronic expansion valve. Therefrigerant evaporating temperature is preferably in the range of about0 to about 10° C. The condensing temperature is preferably in the rangeof about 40 to about 70° C.

The heat transfer composition of the invention is provided for use in amedium temperature refrigeration system, wherein the medium temperaturerefrigeration system is preferably used to chill food or beverages suchas in a refrigerator or a bottle cooler, or in a supermarket to chillperishable goods. The system usually has an air-to-refrigerantevaporator to chill the food or beverage, a reciprocating or rotarycompressor, an air-to-refrigerant condenser to exchange heat with theambient air, and a thermal or electronic expansion valve. Therefrigerant evaporating temperature is preferably in the range of about−12 to about 0° C. The condensing temperature is preferably in the rangeof about 40 to about 70° C. Vending machines are an example of mediumtemperature refrigeration systems.

The heat transfer composition of the invention is provided for use in alow temperature refrigeration system, wherein said low temperaturerefrigeration system is preferably used in a freezer or an ice creammachine. The system usually has an air-to-refrigerant evaporator tochill the product, a reciprocating or rotary compressor, anair-to-refrigerant condenser to exchange heat with the ambient air, anda thermal or electronic expansion valve. The refrigerant evaporatingtemperature is preferably in the range of about −40 to about −12° C. Thecondensing temperature is preferably in the range of about 40 to about70° C.

The heat transfer composition of the invention is provided for use in acascade refrigeration system, wherein said cascade refrigeration systemis preferably used in applications where there is a large temperaturedifference (e.g. about 60-80° C., such as about 70-75° C.) between theambient temperature and the box temperature (e.g. the difference intemperature between the air-side of the condenser in the high stage, andthe air-side of the evaporator in the low stage). For example, a cascadesystem may be used for freezing products in a supermarket.

Each of the heat transfer compositions described herein is particularlyprovided for use in a vending machine having an evaporator temperaturein the range of about −20 to about 10° C., particularly −7° C.

Each of the heat transfer compositions described herein is particularlyprovided for use in a residential heat pump, such as a residential airto water heat pump hydronic system, having an evaporator temperature inthe range of about −20 to about 3° C., particularly about 0.5° C.

Each of the heat transfer compositions described herein is particularlyprovided for use in a medium temperature refrigeration system (with anevaporator temperature in the range of about −12 to about 0° C.,particularly about −7 C).

Each of the heat transfer compositions described herein is particularlyprovided for use in a water heater heat pump having an evaporatortemperature in the range of from about −20° C. to about 25° C.

Each of the heat transfer compositions described herein is particularlyprovided for use in a dehumidifier having an evaporator temperature inthe range of from about 0 to about 10° C.

Each of the heat transfer compositions described herein is particularlyprovided for use in a air cooled chiller having an evaporatortemperature in the range of about 0° C. to about 10° C., particularlyabout 4.5° C. The air cooled chiller may be an air cooled chiller with acentrifugal compressor or an air cooled chiller with a positivedisplacement compressor, more particularly an air cooled chiller with areciprocating or scroll compressor.

Each of the heat transfer compositions described herein is particularlyprovided for use in a water cooled chiller having an evaporatortemperature in the range of about 0° C. to about 10° C., particularlyabout 4.5° C. The air cooled chiller may be an air cooled chiller with acentrifugal compressor or an air cooled chiller with a positivedisplacement compressor, more particularly an air cooled chiller with areciprocating or scroll compressor.

Each of the heat transfer compositions described herein is particularlyprovided for use in a refrigerator having an evaporator temperature inthe range of about −40° C. to about 12° C.

Each of the heat transfer compositions described herein is particularlyprovided for use in a freezer having an evaporator temperature in therange of about −40° C. to about −12° C.

Each of the heat transfer compositions described herein is particularlyprovided for use in a cascade refrigeration system (having a high stagerefrigerant and a low stage refrigerant). The heat transfer compositionsof the invitation are used as the high stage refrigerant in the cascadesystem (which generally has an evaporator temperature in the range ofabout −20 to about 10° C., particularly about −7° C.).

Thus, the invention relates to a method of cooling in a heat transfersystem comprising an evaporator, a condenser and a compressor, and anyrefrigerant of the present invention as described herein, includingparticularly Refrigerants 1-23, Refrigerants 1NF-23NF, Refrigerants1GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, or any of the heattransfer compositions as described herein, the process comprising thesteps of i) condensing the refrigerant, and ii) evaporating therefrigerant in the vicinity of body or article to be cooled, wherein theevaporator temperature of the heat transfer system is in the range offrom about −40° C. to about 10° C.

The invention also relates to a method of cooling in a heat transfersystem comprising an evaporator, a condenser and a compressor, and aheat transfer composition comprising any refrigerant of the presentinvention as described herein, including particularly Refrigerants 1-23,Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, or any of the heat transfer compositions as describedherein, the process comprising the steps of i) condensing therefrigerant, and ii) evaporating the refrigerant in the vicinity of bodyor article to be cooled, wherein the evaporator temperature of the heattransfer system is in the range of from about −40° C. to about 10° C.,wherein said said heat transfer composition further comprises anystabilizer as described herein, including in particular Stabilizer 1 orStabilizer 2.

The invention also relates to a method of cooling in a heat transfersystem comprising an evaporator, a condenser and a compressor, and aheat transfer composition comprising any refrigerant of the presentinvention as described herein, including particularly Refrigerants 1-23,Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, or any of the heat transfer compositions as describedherein, the process comprising the steps of i) condensing therefrigerant, and ii) evaporating the refrigerant in the vicinity of bodyor article to be cooled, wherein the evaporator temperature of the heattransfer system is in the range of from about −40° C. to about 10° C.,wherein said said heat transfer composition further comprises anylubricant as described herein, including in particular Lubricant 1.

The invention also relates to a method of cooling in a heat transfersystem comprising an evaporator, a condenser and a compressor, and aheat transfer composition comprising any refrigerant of the presentinvention as described herein, including particularly Refrigerants 1-23,Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, or any of the heat transfer compositions as describedherein, the process comprising the steps of i) condensing therefrigerant, and ii) evaporating the refrigerant in the vicinity of bodyor article to be cooled, wherein the evaporator temperature of the heattransfer system is in the range of from about −40° C. to about 10° C.,wherein said heat transfer composition further comprises any stabilizeras described herein, including in particular Stabilizer 1 or Stabilizer2 and any lubricant as described herein, including in particularLubricant 1.

Thus, the invention relates to a method of cooling in a heat transfersystem comprising an evaporator, a condenser and a compressor, and anyrefrigerant of the present invention as described herein, includingparticularly Refrigerants 1-23, Refrigerants 1 NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5, or any of the heattransfer compositions as described herein, the process comprising thesteps of i) condensing the refrigerant, and ii) evaporating therefrigerant in the vicinity of body or article to be cooled, wherein theevaporator temperature of the heat transfer system is in the range offrom about −20° C. to about 3° C.

The invention also relates to a method of cooling in a heat transfersystem comprising an evaporator, a condenser and a compressor, and aheat transfer composition comprising any refrigerant of the presentinvention as described herein, including particularly Refrigerants 1-23,Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, or any of the heat transfer compositions as describedherein, the process comprising the steps of i) condensing therefrigerant, and ii) evaporating the refrigerant in the vicinity of bodyor article to be cooled, wherein the evaporator temperature of the heattransfer system is in the range of from about −20° C. to about 3° C.,wherein said said heat transfer composition further comprises anystabilizer as described herein, including in particular Stabilizer 1 orStabilizer 2.

The invention also relates to a method of cooling in a heat transfersystem comprising an evaporator, a condenser and a compressor, and aheat transfer composition comprising any refrigerant of the presentinvention as described herein, including particularly Refrigerants 1-23,Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, or any of the heat transfer compositions as describedherein, the process comprising the steps of i) condensing therefrigerant, and ii) evaporating the refrigerant in the vicinity of bodyor article to be cooled, wherein the evaporator temperature of the heattransfer system is in the range of from about −20° C. to about 3° C.,wherein said said heat transfer composition further comprises anylubricant as described herein, including in particular Lubricant 1.

The invention also relates to a method of cooling in a heat transfersystem comprising an evaporator, a condenser and a compressor, and aheat transfer composition comprising any refrigerant of the presentinvention as described herein, including particularly Refrigerants 1-23,Refrigerants 1 NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, or any of the heat transfer compositions as describedherein, the process comprising the steps of i) condensing therefrigerant, and ii) evaporating the refrigerant in the vicinity of bodyor article to be cooled, wherein the evaporator temperature of the heattransfer system is in the range of from about −20° C. to about 3° C.,wherein said heat transfer composition further comprises any stabilizeras described herein, including in particular Stabilizer 1 or Stabilizer2 and any lubricant as described herein, including in particularLubricant 1.

The heat transfer composition disclosed herein is provided as anon-flammable and low Global Warming (GWP) retrofit for the refrigerantR-134a. Each of the heat transfer compositions of the present invention,including heat transfer compostions which includes any one of therefrigerants of the present invention as described herein, includingparticularly any one of Refrigerants 1-23, Refrigerants 1 NF-23NF,Refrigerants 1 GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150,Refrigerants 1 GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5,therefore can be used in a method of retrofitting an existing heattransfer system designed to contain or containing R-134a refrigerant. Itis preferred that the method does not require substantial engineeringmodification of the existing system, for example, without modificationof the condenser, the evaporator and/or the expansion valve.

As the term is used herein, “retrofit” with respect to a particular heattransfer composition of the present invention means the use of theindicated composition of the present invention in a heat transfer systemthat had contained therein a different refrigerant composition that hadbeen at least partially removed from the system and in which theindicated composition of the present invention is introduced.

The heat transfer composition disclosed herein is provided as anon-flammable and low Global Warming (GWP) replacement for therefrigerant R-134a. Each of the heat transfer compositions of thepresent invention, including heat transfer compostions which includesany one of the refrigerants of the present invention as describedherein, including particularly any one of Refrigerants 1-23,Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants 1 GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, therefore can be used as a replacement for R-134arefrigerant, and it is preferred that the method does not requiresubstantial engineering modification of the system, for example, withoutmodification of the condenser, the evaporator and/or the expansionvalve.

As the term is used herein, “replacement for” with respect to aparticular heat transfer composition of the present invention and aparticular existing refrigerant means the use of the indicatedcomposition of the present invention in a heat transfer system thatheretofore had been commonly used with that existing refrigerant. By wayof example, the heat transfer systems that have heretofore been commonlyused with R-134a include the following systems and the representativeoperating characteristic of evaporator temperature:

R-134a SYSTEMS Evaporator Temp. Range, ° C. (all values understood to beSystem preceeded by “about” Low −40° C. to 12° C. ternperaturerefrigeration Medium −12° C. to 0° C. ternperature refrigeration HeatPumps −12° C. to 10° C.; (including water heater heat pumps) Heat Pumps−20° C. to 3° C.; (including residential heat pumps) Dehumidifier −0° C.to 10° C.; Vending −12° C. to 10° C. machines Chillers 0° C. to 10° C.Refrigerators −40° C. to 2° C. Freezers −40° C. to −12° C.

Alternatively, the heat transfer composition can be used in a method ofretrofitting an existing heat transfer system designed to contain orcontaining R134a refrigerant, wherein the system is modified for therefrigerant of the invention.

It will be appreciated that when the heat transfer composition is usedas a non-flammable and low Global Warming replacement for R-134a or isused in a method of retrofitting an existing heat transfer systemdesigned to contain or containing R134a refrigerant or is used in a heattransfer system which is suitable for use with R134a refrigerant, theheat transfer composition may consist essentially of any the refrigerantof the invention as descried herein, including in particularRefrigerants 1-23, Refrigerants 1 NF-23NF, Refrigerants1GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5. Alternatively, theinvention encompasses the use of the refrigerant of the invention as anon-flammable and low Global Warming replacement for R-134a or is usedin a method of retrofitting an existing heat transfer system designed tocontain or containing R134a refrigerant or is used in a heat transfersystem which is suitable for use with R134a refrigerant as describedherein.

As set out above, the method comprises removing at least a portion ofthe existing R-134a refrigerant from the system. Preferably, the methodcomprises removing at least about 5%, about 10%, about 25%, about 50% orabout 75% by weight of the R-134a from the system and replacing it withthe heat transfer compositions of the invention, including in particularthose heat transfer compositions which include in particularRefrigerants 1-23, Refrigerants 1NF-23NF, Refrigerants 1GWP150-23GWP150,Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1 GWP5-12GWP5, andRefrigerants 1NFGWP5-12NFGWP5.

The compositions of the invention may be employed in systems which areused or are suitable for use with R-134a refrigerant, such as existingor new heat transfer systems.

The refrigerants and heat transfer compositions of the present inventionexhibit many of the desirable characteristics of R-134a, such asnon-flammability, but have a GWP that is substantially lower than thatof R-134a while at the same time having operating characteristics i.e.efficiency (COP), that are substantially similar to or substantiallymatch R-134a.

The refrigerants of the present invention, including in particularRefrigerants 1-23, Refrigerants 1 NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5, therefore preferablyexhibit operating characteristics compared with R134a wherein:

-   -   the efficiency (COP) of the refrigerant is from 95 to 105% of        the efficiency of R134a.

in heat transfer systems, in which the refrigerant of the inventionreplaces the R134a refrigerant.

The term “COP” is a measure of energy efficiency and means the ratio ofrefrigeration or cooling capacity to the energy requirement of therefrigeration system, i.e. the energy to run the compressor, fans, etc.COP is the useful output of the refrigeration system, in this case therefrigeration capacity or how much cooling is provided, divided by howpower it takes to get this output. Essentially, it is a measure of theefficiency of the system.

The term “capacity” is the amount of cooling provided, in BTUs/hr, bythe refrigerant in the refrigeration system. This is experimentallydetermined by multiplying the change in enthalpy in BTU/lb, of therefrigerant as it passes through the evaporator by the mass flow rate ofthe refrigerant. The enthalpy can be determined from the measurement ofthe pressure and temperature of the refrigerant. The capacity of therefrigeration system relates to the ability to maintain an area to becooled at a specific temperature.

The term “mass flow rate” is the amount “in pounds” of refrigerantpassing through a conduit of a given size in a given amount of time.

In order to maintain reliability of the heat transfer system, it ispreferred that the refrigerant of the invention, including in particularRefrigerants 1-23, Refrigerants 1 NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5, further exhibits thefollowing characteristics compared with R-134a:

-   -   the discharge temperature is not greater than 10° C. higher than        that of R-134a; and/or    -   the compressor pressure ratio is from 95 to 105% of the        compressor pressure ratio of R-134a

in heat transfer systems, in which the composition of the invention isused to replace the R-134a refrigerant.

It will be appreciated by the skilled person that the claimedcompositions desirably show a low level of glide. Thus, the refrigerantsof present invention, including in particular Refrigerants 1-23,Refrigerants 1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants 1 GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, provide an evaporator glide of less than 2° C.,preferably less than 1.5° C.

The existing heat transfer compositions used with R-134a are preferablyrefrigeration systems. Thus, each of the heat transfer compositions asdescribed herein can be used to replace R134a in in any one of:

-   -   a low temperature refrigeration system,    -   a medium temperature refrigeration system,    -   a commercial refrigerator,    -   a commercial freezer,    -   a cascade refrigeration system,    -   an ice machine,    -   a vending machine,    -   a domestic freezer,    -   a domestic refrigerator,    -   an industrial freezer,    -   an industrial refrigerator    -   a water cooler or    -   a chiller.

The refrigerants of the invention, including in particular Refrigerants1-23, Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150,Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1 GWP5-12GWP5, andRefrigerants 1 NFGWP5-12NFGWP5, are provided to replace R134a in heatpump applications. Thus, each of the heat transfer compositions andrefrigerants as described herein, including an of Refrigerants 1-23,Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants 1 GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5 can be used to replace R-134a in any one of:

-   -   a residential heat pump, such as a residential air to water heat        pump/hydronic system,    -   an industrial heat pump system or    -   a commercial heat pump system.

Each of the heat transfer compositions and refrigerants as describedherein, including in particular any one of Refrigerants 1-23,Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, is particularly provided to replace R134a in an aircooled chiller (with an evaporator temperature in the range of about 0to about 10° C., particularly about 4.5° C.), particularly an air cooledchiller with a centrifugal or positive displacement compressor, e.g. anair cooled chiller with a reciprocating or scroll compressor.

Each of the heat transfer compositions and refrigerants describedherein, including in particular each of Refrigerants 1-23, Refrigerants1 NF-23NF, Refrigerants 1 GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, is particularly provided to replace R134a in a watercooled chiller (with an evaporator temperature in the range of about 0to about 10° C., particularly about 4.5° C.), particularly a watercooled chiller with a centrifugal or positive displacement compressor,e.g. a water cooled chiller with a reciprocating or scroll compressor.

Each of the heat transfer compositions and each of the refrigerantsdescribed herein, in particular any one of Refrigerants 1-23,Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants 1 GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, is particularly provided to replace R134a in aresidential heat pump, such as a residential air to water heat pumphydronic system (with an evaporator temperature in the range of about−20 to about 3° C., particularly about 0.5° C.).

Each of the heat transfer compositions and refrigerants as describedherein, including any one of Refrigerants 1-23, Refrigerants 1 NF-23NF,Refrigerants 1 GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150,Refrigerants 1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, isparticularly provided to replace R134a in a medium temperaturerefrigeration system (with an evaporator temperature in the range ofabout −12 to about 0° C., particularly about −7° C.).

Each of the heat transfer compositions and refrigerants describedherein, including in particular any one of Refrigerants 1-23,Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, is particularly provided to replace R134a in a lowtemperature refrigeration system (with an evaporator temperature in therange of about −40 to about −12° C., particularly about −32° C.).

Each of the heat transfer compositions and refrigerants describedherein, in particular any one of Refrigerants 1-23, Refrigerants 1NF-23NF, Refrigerants 1 GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, is particularly provided to replace R134a in the highstage of a cascade refrigeration system (where the high stage of thecascade system has an evaporator temperature in the range of about −20to about 10° C., particularly about −7° C.).

The heat transfer compositions and the refrigerants of the invention,including in particular any one of Refrigerants 1-23, Refrigerants 1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, is provided for use in a residential heat pump system,wherein the residential heat pump system is used to supply warm air(said air having a temperature of for example, about 18° C. to about 24°C., particularly about 21° C.) to buildings in the winter. It is usuallythe same system as the residential air-conditioning system, while in theheat pump mode the refrigerant flow is reversed and the indoor coilbecomes condenser and the outdoor coil becomes evaporator. Typicalsystem types are split and mini-split heat pump system. The evaporatorand condenser are usually a round tube plate fin, a finned ormicrochannel heat exchanger. The compressor is usually a reciprocatingor rotary (rolling-piston or rotary vane) or scroll compressor. Theexpansion valve is usually a thermal or electronic expansion valve. Therefrigerant evaporating temperature is preferably in the range of about−20 to about 3° C. or about −30 to about 5° C. The condensingtemperature is preferably in the range of about 35 to about 50° C.

The heat transfer composition and refrigerants of the invention,including in particular any one of Refrigerants 1-23, Refrigerants1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, is provided for use in a commercial air-conditioningsystem wherein the commercial air conditioning system can be a chillerwhich is used to supply chilled water (said water having a temperatureof for example about 7° C.) to large buildings such as offices andhospitals, etc.

Depending on the application, the chiller system may be running all yearlong. The chiller system may be air-cooled or water-cooled. Theair-cooled chiller usually has a plate, tube-in-tube or shell-and-tubeevaporator to supply chilled water, a reciprocating or scrollcompressor, a round tube plate fin, a finned tube or microchannelcondenser to exchange heat with ambient air, and a thermal or electronicexpansion valve. The water-cooled system usually has a shell-and-tubeevaporator to supply chilled water, a reciprocating, scroll, screw orcentrifugal compressor, a shell-and-tube condenser to exchange heat withwater from cooling tower or lake, sea and other natural recourses, and athermal or electronic expansion valve. The refrigerant evaporatingtemperature is preferably in the range of about 0 to about 10° C. Thecondensing temperature is preferably in the range of about 40 to about70° C.

The heat transfer composition and the refrigerants of the invention,including in particular any one of Refrigerants 1-23, Refrigerants 1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, is provided for use in a residential air-to-water heatpump hydronic system, wherein the residential air-to-water heat pumphydronic system is used to supply hot water (said water having atemperature of for example about 50° C. or about 55° C.) to buildingsfor floor heating or similar applications in the winter. The hydronicsystem usually has a round tube plate fin, a finned tube or microchannelevaporator to exchange heat with ambient air, a reciprocating, scroll orrotary compressor, a plate, tube-in-tube or shell-in-tube condenser toheat the water, and a thermal or electronic expansion valve. Therefrigerant evaporating temperature is preferably in the range of about−20 to about 3° C., or −30° C. to about 5° C. The condensing temperatureis preferably in the range of about 50° C. to about 90° C.

Each of the heat transfer compositions and the refrigerants of theinvention, including in particular any one Refrigerants 1-23,Refrigerants 1 NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, is particularly provided for use in a mediumtemperature refrigeration system. Medium temperature refrigerationsystems utilize one or more compressors and a condenser temperature offrom about 20° C. to about 60° C. and preferably about 25° C. to about45° C. Medium temperature refrigeration systems have an evaporatortemperature of from about −25° C. to less than about 0° C., morepreferably from about −20° C. to about −5° C., and most preferably about−10° C. to about −6.7° C. Moreover, in preferred embodiments of suchmedium temperature refrigeration systems, the systems have a degree ofsuperheat at the evaporator outlet of from about 0° C. to about 10° C.,and preferably with a degree of superheat at the evaporator outlet offrom about 4° C. to about 6° C. Furthermore, in preferred embodiments ofsuch systems, medium temperature refrigeration systems have a degree ofsuperheat in the suction line of from about 5° C. to about 40° C., andmore preferably about 15° C. to about 30° C.

Each of the heat transfer compositions and the refrigerants of theinvention, including in particular each of Refrigerants 1-23,Refrigerants 1 NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, is particularly provided for use in a low temperaturerefrigeration. Low temperature refrigeration systems utilize one or morecompressors and a condenser temperature of from about 20° C. to about60° C. and preferably from about 25° C. to about 45° C. Low temperaturerefrigeration systems have an evaporator temperature of from about −45°C. to less than about 0° C., more preferably from about −40 to about−12° C., even more preferably from about −35° C. to about −25° C., andmost preferably about −32° C. Moreover, preferably, the low temperaturerefrigeration systems have a degree of superheat at evaporator outlet offrom about 0° C. to about 10° C., and preferably with a degree ofsuperheat at evaporator outlet of from about 4° C. to about 6° C.Furthermore, preferably, low temperature refrigeration systems have adegree of superheat in the suction line of from about 15° C. to about50° C., and preferably with a degree of superheat in the suction line offrom about 25° C. to about 30° C.

The heat transfer composition and the refrigerants of the invention,including in particular each of Refrigerants 1-23, Refrigerants 1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, is provided for use in a medium temperaturerefrigeration system, wherein the medium temperature refrigerationsystem is preferably used to chill food or beverages such as in arefrigerator or a bottle cooler. The system usually has anair-to-refrigerant evaporator to chill the food or beverage, areciprocating, scroll or screw or rotary compressor, anair-to-refrigerant condenser to exchange heat with the ambient air, anda thermal or electronic expansion valve.

The heat transfer composition and the refrigerants of the invention,including in particular each of Refrigerants 1-23, Refrigerants 1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants1NFGWP5-12NFGWP5, is provided for use in a low temperature refrigerationsystem, wherein said low temperature refrigeration system is preferablyused in a freezer or an ice making machine. The system usually has anair-to-refrigerant evaporator to chill the food or beverage, areciprocating, scroll or rotary compressor, an air-to-refrigerantcondenser to exchange heat with the ambient air, and a thermal orelectronic expansion valve.

EXAMPLES

The refrigerant compositions identified in Table 1A and Table 1B belowwere analyzed as described herein. Each composition was subjected tothermodynamic analysis to determine its ability to match the operatingcharacteristics of R-134a in various refrigeration systems. The analysiswas performed using experimental data collected for properties ofvarious binary pairs of components used in the composition. Thevapor/liquid equilibrium behavior of CF₃I was determined and studied ina series of binary pairs with each of HFCO-1233zd(E), HFO-1234ze(E) andHFC-227ea. The vapour liquid equilibrium behavior of CF3I was studied ina series of binary pairs with HFCO-1233zd(E) and HFC-227ea. The vapourliquid equilibrium behavior of the binary pairs of HFCO-1233zd(E) andHFC-227ea was also studied. The composition of each binary pair wasvaried over a series of relative percentages in the experimentalevaluation and the mixture parameters for each binary par were regressedto the experimentally obtained data. Data for individual components isavailable in the National Institute of Science and Technology (NIST)Reference Fluid Thermodynamic and Transport Properties Database software(Refprop 9.1 NIST Standard Database 2013) and was as needed in theExamples. The parameters selected for conducting the analysis were: samecompressor displacement for all refrigerants, same operating conditionsfor all refrigerants, same compressor isentropic and volumetricefficiency for all refrigerants. In each Example, simulations wereconducted using the measured vapor liquid equilibrium data. Thesimulation results are reported for each Example.

TABLE 1A Refrigerants of the invention R1234ze(E) R1233zd(E) CF3IRefrigerant (wt %) (wt %) (wt %) Al 78.0% 1.0% 21.0% A2 77.0% 2.0% 21.0%A3 78.0% 2.0% 20.0% A4 80.0% 2.0% 18.0% A5 82.0% 2.0% 16.0% A6 83.0%2.0% 15.0%

TABLE 1B Refrigerants of the invention R1234ze(E) R1233zd(E) HFC-227eaCF3I Refrigerant (wt %) (wt %) (wt %) (wt %) B1 87.0% 2.0% 4.4%  6.6% B284.0% 2.0% 4.4%  9.6% B3 81.0% 2.0% 4.4% 12.6% B4 78.0% 2.0% 4.4% 15.6%B5 75.0% 2.0% 4.4% 18.6%

Example 1A: Thermodynamic Glide

In systems containing direct expansion evaporators, the evaporatormanufacturer generally sets a design limit of a pressure drop which isequivalent to a loss of 1° C. to 2° C. in saturation temperature fromthe inlet to the outlet of the evaporator (Encyclopedia of Two Phaseheat transfer and Flow I, John T Thome, chapter 6, p144).

The saturation temperature in the evaporator tends to increase forrefrigerants with glide. This increase in temperature is equal to theglide of the refrigerant in the evaporator. The actual temperaturevariation in the evaporator is the net effect of both of theseprocesses. Therefore, a refrigerant with a glide of less than 2° C. inthe evaporator will have an almost constant temperature in theevaporator. This will lead to a very efficient heat exchanger design,especially for applications such as reversible heat pumps where therefrigerant flow changes direction in the heat exchanger, depending onthe mode of operation (i.e. heating or cooling).

The thermodynamic glide was determined by experimentally measuring theinteraction parameters with the binary pairs of refrigerants(HFO-1234ze(E)/HFCO-1233zd(E), HFO-1234ze(E)/CF₃I, HFCO-1233zd(E)/CF₃I)and using NIST Refprop 9.1 for calculating the difference in bubble(liquid) and dew (vapor) temperatures.

The observed glide was unexpectedly lower than predicted by the NISTRefprop 9.1 database which uses estimated interaction parameters(without experimental data) between the binary pairs.

TABLE 2 Thermodynamic glide of Refrigerant A2 Blend A2(R1234ze(E)/R1233zd(E)/CF3I 78%/2%/20%) Thermodynamic glideThermodynamic glide with with binary interaction Temperature modeledbinary interaction determined (° C.) (° C.) experimentally (° C.) 40 1.81.3 10 2.4 1.7 0 2.6 1.8 −10 2.9 2.0

The above data demonstrates that the claimed compositions have a lowerglide than predicted by modelling without taking into account theunpredictable interaction between the three components of the blend.

Example 1B: Thermodynamic Glide

The procedure of Example 1A is repeated except of the compositon B2. Thethermodynamic glide was determined by experimentally measuring theinteraction parameters with the binary pairs of refrigerants(HFO-1234ze(E)/HFCO-1233zd(E), HFO-1234ze(E)/CF₃I,HFO-1234ze(E)/HFC-227ea, HFCO-1233zd(E)/CF₃I, HFC-227ea/CF₃I,HFCO-1233zd(E)/HFC-227ea) and using NIST Refprop 9.1 for calculating thedifference in bubble (liquid) and dew (vapor) temperatures.

The observed glide was unexpectedly lower than predicted by the NISTRefprop 9.1 database which uses estimated interaction parameters(without experimental data) between the binary pairs.

TABLE 2 Thermodynamic glide of Refrigerant B2 Blend B2(R1234ze(E)/R227ea/CF3I/R1233zd(E) 84%/4.4%/9.6%/2%) Thermodynamic glideThermodynamic glide with with binary interaction Temperature modeledbinary interaction determined (° C.) (° C.) experimentally (° C.) 40 1.41.1 10 1.9 1.4 0 2.0 1.5 −10 2.2 1.6

The above data demonstrates that the claimed compositions have a lowerglide than predicted by modelling without taking into account theunpredictable interaction between the four components of the blend.

Example 2A: Flammability

Both CF₃I and HFCO-1233zd(E) are known to be non-flammable refrigerants,and can act to suppress the flammability of refrigerant blends whichcontain flammable components.

As set out in Table 3A below, a binary composition containingHFO-1234ze(E) and CF₃I requires at least 35% of CF₃I in order to renderthe composition non-flammable. Furthermore, a binary compositioncontaining HFCO-1233zd(E) and HFO-1234ze(E) requires at least 31% ofHFCO-1233zd(E) to render the composition non-flammable. However, theinventors have surprisingly discovered that when CF₃I and HFCO-1233zd(E)are both used, the composition requires much less of these components inorder to be non-flammable. For example, a composition containing 20% ofa combination of HFCO-1233zd(E) and CF₃I is non-flammable.

TABLE 3A Assessment of flammability Refrigerant Flammability %R1234ze(E) % R1233zd(E) % CF3I Comparative Non-flammable 69% 31% — C1Comparative Non-flammable 65% — 35% C2 A3 Non-flammable 80%  2% 18%

Example 2B: Flammability

HFC-227ea, CF₃I and HFCO-1233zd(E) are known to be non-flammablerefrigerants. CF₃I and HFCO-1233zd(E) can act to suppress theflammability of refrigerant blends which contain flammable components.

As set out in Table 3B below, a binary composition containingHFO-1234ze(E) and CF₃I requires at least 35% of CF₃I in order to renderthe composition non-flammable. Furthermore, a binary compositioncontaining HFCO-1233zd(E) and HFO-1234ze(E) requires at least 31% ofHFCO-1233zd(E) to render the composition non-flammable.

While a binary composition of R-227ea and R1234ze(E) requires 12% ofR227ea in order to render the composition non-flammable, thiscomposition has a GWP of 403, and therefore does not meet therequirements of the preferred embodiments of the invention, that is, anon-flammable composition having a GWP of less than 150.

However, the inventors have surprisingly discovered that when R227ea,CF₃I and HFCO-1233zd(E) are all used with HFO1234ze(E), the compositionrequires a much smaller amount of these components in order to benon-flammable, as compared to using CF₃I or HFCO-1233zd(E) alone. Forexample, a composition containing 15% of a combination ofHFCO-1233zd(E), CF₃I is non-flammable, while at the same time having aGWP of less than 150.

TABLE 3 Assessment of flammability Flamm- % % % % Refrigerant abilityR1234ze(E) R1233zd(E) CF3I R227ea Comp- Non- 69% 31% — arative flammableCl Comp- Non- 65% —  35% arative flammable C2 Comp- Non- 88% — —  12%arative flammable C3 B2 Non- 84%  2% 9.6% 4.4% flammable

Example 3: Performance Example 3A: Performance in a CO₂ CascadeRefrigeration System

Cascade systems are generally used in applications where there is alarge temperature difference (e.g. about 60-80° C., such as about 70-75°C.) between the ambient temperature and the box temperature (e.g. thedifference in temperature between the air-side of the condenser in thehigh stage, and the air-side of the evaporator in the low stage). Forexample, a cascade system may be used for freezing products in asupermarket.

In the following Example, exemplary compositions of the invention weretested as the refrigerant in the high stage of a cascade refrigerationsystem. The refrigerant used in the low stage of the system was carbondioxide. A schematic of an exemplary cascade system is shown in FIG. 4and the results are reported in Table 4A.

Operating conditions:

-   -   1. Condensing temperature=45° C.    -   2. Condensing Temperature—Ambient Temperature=10° C.    -   3. Condenser sub-cooling=0.0° C. (system with receiver)    -   4. Evaporating temperature=−30° C., Corresponding box        temperature=−18° C.    -   5. Evaporator Superheat=3.3° C.    -   6. Compressor Isentropic Efficiency=65%    -   7. Volumetric Efficiency=100%    -   8. Temperature Rise in Suction Line Low Stage=15° C.    -   9. Temperature Rise in Suction Line High Stage=10° C.    -   10. Intermediate Heat Exchanger CO₂ Condensing Temperature=15°        C., 20° C. and 25° C.    -   11. Intermediate Heat Exchanger Superheat=3.3° C.    -   12. Difference in Temperature in Intermediate Heat Exchanger=8°        C.

TABLE 4 Performance in CO2 Cascade Refrigeration System Efficiency @Efficiency @ Efficiency @ Refrigerant Tcond = 15° C. Tcond = 20° C.Tcond = 25° C. R134a 100% 100% 100% Al 100% 101% 101% A2 100% 101% 101%A3 100% 101% 101% A4 100% 101% 101% A5 100% 101% 101% A6 100% 101% 101%

-   -   Table 4A shows the performance of refrigerants A1 to A5 in the        high side of a cascade refrigeration system    -   Composition A1 to A5 match the efficiency of R134a for different        condensing temperatures of the low stage cycle

Example 3B: CO₂ Cascade Refrigeration System

Example 3A is repeated except using compositions E1-B5 and with theadjustment of the operating conditions as indicated below:

Operating conditions:

-   -   1. Condensing temperature=45° C.    -   2. Condensing Temperature—Ambient Temperature=10° C.    -   3. Condenser sub-cooling=0.0° C. (system with receiver)    -   4. Evaporating temperature=−30° C., Corresponding box        temperature=−18° C.    -   5. Evaporator Superheat=3.3° C.    -   6. Compressor Isentropic Efficiency=65%    -   7. Volumetric Efficiency=100%    -   8. Temperature Rise in Suction Line Low Stage=15° C.    -   9. Temperature Rise in Suction Line High Stage=10° C.    -   10. Intermediate Heat Exchanger CO₂ Condensing Temperature=15°        C., 20° C. and 25° C.    -   11. Intermediate Heat Exchanger Superheat=3.3° C.    -   12. Difference in Temperature in Intermediate Heat Exchanger=8°        C.

The results are reported in Table 4B below.

TABLE 4B Performance in CO2 Cascade Refrigeration System Efficiency @Efficiency @ Efficiency @ Refrigerant Tcond = 15° C. Tcond = 20° C.Tcond = 25° C. R134a 100% 100% 100% B1 100% 100% 101% B2 100% 100% 101%B3 100% 100% 101% B4 100% 100% 101% B5 100% 100% 101%

-   -   The results are reported in Table 4B below.    -   Table 4B shows the performance of exemplary refrigerants of the        invention in a cascade refrigeration system.    -   Composition 1 to B5 match the efficiency of R134a at varying        condensing temperatures of low stage cycle.

Example 4A: Performance in Air-Source Heat Pump Water Heaters withSuction Line/Liquid Line Heat Exchanger

The compositions of the invention may be used in a residentialair-to-water heat pump hydronic system. A residential air-to-water heatpump hydronic system is generally used to supply hot water (said waterhaving a temperature of for example about 50° C.) to buildings for floorheating or similar applications in the winter. The hydronic systemusually has a round tube plate fin or microchannel evaporator toexchange heat with ambient air, a reciprocating or rotary compressor, aplate condenser to heat the water, and a thermal or electronic expansionvalve. The refrigerant evaporating temperature is preferably in therange of about −20 to about 3° C. The condensing temperature ispreferably in the range of about 50 to about 90° C.

In the following Example, exemplary compositions of the invention weretested in a heat pump water heater system, with and without a SuctionLine/Liquid Line Heat Exchanger. A schematic of a heat pump water heatersystem, with a Suction Line/Liquid Line Heat Exchanger is shown in FIG.2 and reported in Table 5A below.

Operating conditions:

-   -   1. Condensing temperature=55° C.    -   2. Water Inlet Temperature=45° C., Water Outlet Temperature=50°        C.    -   3. Condenser sub-cooling=5.0° C.    -   4. Evaporating temperature=−5° C., Corresponding ambient        temperature=10° C.    -   5. Evaporator Superheat=3.5° C.    -   6. Compressor Isentropic Efficiency=60%    -   7. Volumetric Efficiency=100%    -   8. Temperature Rise in Suction Line=5° C.    -   9. Suction Line/Liquid Line Heat Exchanger Effectiveness: 0%,        35%, 55%, 75%

TABLE 5A Performance in Heat Pump Water Heaters with SL/LL HX SL-LL HXEff. SL-LL HX Eff. SL-LL HX Eff. No-SL-LL HX 35% 55% 75% Comp. Comp.Comp. Comp. Discharge Discharge Discharge Discharge Temp Temp Temp TempRefrigerant Efficiency (° C.) Efficiency (° C.) Efficiency (° C.)Efficiency (° C.) R134a 100% 92.5 100% 117.9 100% 123.7 100% 134.8 A1100% 84.9 101% 110.3 101% 115.7 102% 126.7 A2 100% 85.4 101% 110.4 101%116.0 102% 126.9 A3 100% 85.2 101% 110.3 101% 115.8 102% 126.7 A4 100%85.0 101% 110.1 101% 115.6 102% 126.5 A5 100% 84.8 101% 109.8 101% 115.3102% 126.2 A6 100% 84.6 101% 109.7 101% 115.2 102% 126.1

-   -   Table 5A shows performance of refrigerants in a heat pump water        heater with and without a suction line/liquid line heat        exchanger (SLLL HX)    -   Composition A1 to A5 show higher efficiency than R134a when a        SLL Heat Exchanger is employed    -   Composition A1 to A5 show lower discharge temperature than        R134a, indicating better reliability for the compressor.

Example 4B: Performance in Air-Source Heat Pump Water Heaters withSuction Line/Liquid Line Heat Exchanger

Example 4B is repeated except using compositions B1-B5, and the resultsare reported in Table 5B below:

TABLE 5B Performance in Heat Pump Water Heaters with SL/LL HX SL-LL HXEff. SL-LL HX Eff. SL-LL HX Eff. No-SL-LL HX 35% 55% 75% Comp. Comp.Comp. Comp. Discharge Discharge Discharge Discharge Temp Temp Temp TempRefrigerant Efficiency (° C.) Efficiency (° C.) Efficiency (° C.)Efficiency (° C.) R134a 100% 92.5 100% 117.9 100% 123.7 100% 134.8 B1100% 82.8 101% 108.0 101% 113.3 102% 124.2 B2 100% 83.1 101% 108.3 101%113.6 102% 124.5 B3 100% 83.5 101% 108.6 101% 114.0 102% 124.9 B4 100%83.9 101% 108.9 101% 114.4 102% 125.2 B5 100% 84.2 101% 109.2 101% 114.7102% 125.6

-   -   Table 5B shows the performance of exemplary refrigerants of the        invention in a heat pump water heater with and without a suction        line/liquid line heat exchanger (SL/LL HX)    -   Composition B1 to B5 show the same efficiency (COP) as R134a in        the system without a SL/LL Heat Exchanger, and a better        efficiency (COP) than R134a when a SL/LL Heat Exchanger is        employed    -   Composition B1 to B5 show lower discharge temperature than        R134a, indicating better reliability for the compressor.

Example 5: Performance in Vending Machines with Suction Line/Liquid LineHeat Exchanger

The compositions of the invention may be used in medium temperaturesystems. A medium temperature refrigeration system is preferably used tochill food or beverages such as in a refrigerator or a bottle cooler, orin a supermarket to chill perishable goods. The system usually has anair-to-refrigerant evaporator to chill the food or beverage, areciprocating or rotary compressor, an air-to-refrigerant condenser toexchange heat with the ambient air, and a thermal or electronicexpansion valve. The refrigerant evaporating temperature is preferablyin the range of about −12 to about 0° C. The condensing temperature ispreferably in the range of about 40 to about 70° C. Vending machines arean example of medium temperature refrigeration systems.

In the following Example, exemplary compositions of the invention weretested in a vending machine system, with and without a SuctionLine/Liquid Line Heat Exchanger, and the results are reported in Table 6below.

Operating conditions:

-   -   1. Condensing temperature=45° C.    -   2. Condensing Temperature—Ambient Temperature=10° C.    -   3. Condenser sub-cooling=5.5° C.    -   4. Evaporating temperature=−8° C., Corresponding box        temperature=1.7° C.    -   5. Evaporator Superheat=3.5° C.    -   6. Compressor Isentropic Efficiency=60%    -   7. Volumetric Efficiency=100%    -   8. Temperature Rise in Suction Line=5° C.    -   9. Suction Line/Liquid Line Heat Exchanger Effectiveness: 0%,        35%, 55%, 75%

TABLE 6 Performance in Vending Machine with SL/LL HX EfficiencyEfficiency Efficiency Efficiency Refrigerant @ 0% @ 35% @ 55% @ 375%R134a 100% 100% 100% 100% Al  99% 101% 101% 102% A2  99% 101% 101% 102%A3  99% 101% 101% 102% A4  99% 101% 101% 102% A5  99% 101% 101% 102% A6 99% 101% 101% 102%

-   -   Table 6 shows performance of refrigerants in a vending machine        system with and without a suction line/liquid line heat        exchanger (SL/LL HX)

Composition A1 to A5 show higher efficiency than R134a when a SL/LL HeatExchanger is employed.

Example 6: Medium Temperature Refrigeration System with SuctionLine/Liquid Line (SL/LL) Heat Exchanger

The compositions of the invention may be used in medium temperaturesystems. A medium temperature refrigeration system is preferably used tochill food or beverages such as in a refrigerator or a bottle cooler, orin a supermarket to chill perishable goods. The system usually has anair-to-refrigerant evaporator to chill the food or beverage, areciprocating or rotary compressor, an air-to-refrigerant condenser toexchange heat with the ambient air, and a thermal or electronicexpansion valve. The refrigerant evaporating temperature is preferablyin the range of about −12 to about 0° C. The condensing temperature ispreferably in the range of about 40 to about 70° C.

In the following Example, exemplary compositions of the invention weretested in a medium temperature refrigeration system, with and without aSuction Line/Liquid Line Heat Exchanger. A schematic of a mediumtemperature refrigeration system, with a Suction Line/Liquid Line HeatExchanger is shown in FIG. 1 and the results are reported in Table 7below.

Operating conditions:

-   -   1. Condensing temperature=45° C.    -   2. Condensing Temperature—Ambient Temperature=10° C.    -   3. Condenser sub-cooling=0.0° C. (system with receiver)    -   4. Evaporating temperature=−8° C., Corresponding box        temperature=1.7° C.    -   5. Evaporator Superheat=5.5° C.    -   6. Compressor Isentropic Efficiency=65%    -   7. Volumetric Efficiency=100%    -   8. Temperature Rise in Suction Line=10° C.    -   9. Suction Line/Liquid Line Heat Exchanger Effectiveness: 0%,        35%, 55%, 75%

TABLE 7 Performance in a Medium-Temperature Refrigeration System withSL/LL HX Efficiency Efficiency Efficiency Efficiency Refrigerant @ 0% @35% @ 55% @ 75% R134a 100% 100% 100% 100% B1 100% 101% 101% 102% B2 100%101% 101% 102% B3 100% 101% 101% 102% B4 100% 101% 101% 102% B5 100%101% 101% 102%

-   -   Table 4 shows the performance of exemplary refrigerants of the        invention in a medium temperature refrigeration system as        compared to R134a    -   Composition B1 to B5 show the same efficiency (COP) as R134a in        the system without a SL/LL Heat Exchanger, and a better        efficiency (COP) than R134a when a SL/LL Heat Exchanger is        employed.

Comparative Example C1: Comparative Cascade System 1B

Table C1 below shows the results of a cascade refrigeration systemdescribed in reference to FIG. 1B both with and without a mechanicalsubcooler in which the refrigerant in the secondary loop and the primaryloop is R404A.

TABLE C1 Medium Low Relative temper- temper- COP % of ature ature R404A(second (first (% of refrig- refrig- R404A eration eration PowerCapacity COP w mech Systems circuit) circuit) [kW] [kW] [−] SC) Compar-R404A 54.8 100 1.823487   100% ative example Compar- 49.6 100 2.016129110.6% ative (100%) example with mechanical subcooler

Table C1 above includes information on the coefficient of performance(COP) of each system. The COP is the ratio of useful cooling output fromthe system to work input to the system. Higher COPs equate to loweroperating costs. The relative COP is the COP relative to the comparativeexample refrigeration system with no subcooling.

Example 7: Cascade System 2

Table 8 below shows the results of a cascade refrigeration systemdescribed in reference to FIG. 2 both with and without a mechanicalsubcooler in which the refrigerant in the secondary loop is each ofrefrigerants A2 and B2 as described above and in which the refrigerantin the primary loop is R404A. The results are reported in Table 8 below,with the results from Comparative Example 1 being repeated in the Tablefor convenience.

TABLE 8 Medium Low Relative temper- temper- COP % of ature ature R404A(second (first (% of refrig- refrig- R404A eration eration PowerCapacity COP w mech circuit) circuit) [kW] [kW] [−] SC) ComparativeR404A 54.8 100 1.82   100% example (FIG. 1B) Comparative 49.6 100 2.02110.6% example with (100%) mechanical subcooler (FIG. 1B) Example 7 A2R744 46.6 100 2.14 117.6% (FIG. 2) (106.3%) B2 R744 46.8 100 2.14 117.2%(106.0%)

It is clear from Table 8 that the cascaded refrigeration circuit whichuses the refrigerants A2 and B2 of the present invention in thesecondary loop in accordance with Cascade System 2 (FIG. 2) achieves thelowest power consumption and the best COP compared to the comparativesystems.

The results shown in Tables C1 and 8 are based on the below assumptions,where MT means medium temperature (second refrigeration circuit) and LTmeans low temperature (first refrigeration circuit) and units are asgiven.

-   -   Load distribution    -   LT: ⅓ (33,000 W)    -   MT: ⅔ (67,000 W)    -   Volumetric efficiency: 95% for both MT ad LT    -   Isentropic efficiency    -   R404A: MT/LT, 0.72/0.68    -   Condensing temperature: 105 F    -   MT evaporation temperature: 20 F (22 F for Self-contained units        due to lower pressure drop)    -   LT evaporation temperature: −25 F    -   Evaporator superheat: 10 F    -   Suction line temperature rise    -   Comparative example: MT: 25 F; LT: 50 F    -   Cascade/self-contained: MT: 10 F; LT: 25 F (Self-contained units        have shorter lines and therefore less heat infiltration)    -   Cascade/pumped: MT: 10 F; LT: 25 F    -   Mechanical sub cooler outlet temperature: 50 F

Example 8: Cascade System 2 with Suction Line Liquid Line Heat Exchanger

Table 9 below shows the results of a cascade refrigeration systemdescribed in reference to FIG. 2 both with and without a mechanicalsubcooler but which in addition has a SLHX installed in the secondrefrigeration loop, with the refrigerant in the secondary loop being inone case refrigerant A2 and in the other case refrigerant B2 asdescribed above and in which the refrigerant in the primary loop isR404A. The results are reported in Table 9 below, with the results fromComparative Example 1 being repeated in the Table for convenience.

TABLE 8 Medium Low Relative temper- temper- COP % of ature ature R404A(second (first (% of refrig- refrig- R404A eration eration PowerCapacity COP w mech circuit) circuit) [kW] [kW] [−] SC) ComparativeR404A 54.8 100 1.82   100% example (FIG. 1B) Comparative 49.6 100 2.02110.6% example with (100%) mechanical subcooler (FIG. 1B) Example 7 A2R744 43.97 100 2.27 124.7% (FIG. 2) (112.8%) B2 R744 43.98 100 2.27124.7% (112.8%)

It is clear from Table 8 that the cascaded refrigeration circuit whichuses the refrigerants A2 and B2 of the present invention in thesecondary loop in accordance with Cascade System 2 (FIG. 2) and ansuction line liquid line heat exchanger (SLHX) achieves the lowest powerconsumption and the best COP compared to the comparative systems and tothe system of FIG. 2 but without the SLHX.

The results shown in Tables C1 and 8 are based on the below assumptions,where MT means medium temperature (second refrigeration circuit) and LTmeans low temperature (first refrigeration circuit) and units are asgiven.

-   -   Load distribution    -   LT: ⅓ (33,000 W)    -   MT: ⅔ (67,000 W)    -   Volumetric efficiency: 95% for both MT ad LT    -   Isentropic efficiency    -   R404A: MT/LT, 0.72/0.68    -   Condensing temperature: 105 F    -   MT evaporation temperature: 20 F (22 F for Self-contained units        due to lower pressure drop)    -   LT evaporation temperature: −25 F    -   Evaporator superheat: 10 F    -   Suction line temperature rise    -   Comparative example: MT: 25 F; LT: 50 F    -   Cascade/self-contained: MT: 10 F; LT: 25 F (Self-contained units        have shorter lines and therefore less heat infiltration)    -   Cascade/pumped: MT: 10 F; LT: 25 F    -   Mechanical sub cooler outlet temperature: 50 F

Numbered Embodiment 1

A refrigerant comprising at least about 97% by weight of the followingthree compounds, with each compound being present in the followingrelative percentages of:

from 1% by weight to 3% by weight trans-1-chloro-3,3,3-trifluoropropene(HFCO-1233zd(E),

from about 77% by weight to about 83% by weighttrans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E), and

from about 15% by weight to about 21% by weight trifluoroiodomethane(CF3I).

Numbered Embodiment 2

The refrigerant of numbered embodiment 1 wherein the refrigerant ofthree compounds is: from 1% by weight to 3% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E),

from about 77% by weight to about 83% by weighttrans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E), and

from about 18% by weight to about 21% by weight trifluoroiodomethane(CF3I).

Numbered Embodiment 3

The refrigerant of numbered embodiment 1 or numbered embodiment 2wherein the refrigerant of three compounds is

from 1% by weight to 3% by weight HFCO-1233zd(E),

from about 77% by weight to about 80% by weight HFO-1234ze(E), and

from about 18% by weight to about 21% by weight trifluoroiodomethane(CF3I).

Numbered Embodiment 4

The refrigerant of any one of numbered embodiments 1 to 3 wherein theHFCO-1233zd(E) is present in an amount of 2%+/−0.5% by weight of thecomposition.

Numbered Embodiment 5

The refrigerant of any one of numbered embodiments 1 to 4 wherein therefrigerant of three compounds is

2%+/−0.5% by weight HFCO-1233zd(E),

about 78% by weight HFO-1234ze(E), and

about 20% by weight trifluoroiodomethane (CF3I).

Numbered Embodiment 6

The refrigerant of any one of numbered embodiments 1 to 5 wherein therefrigerant of three compounds is

2%+/−0.5% by weight HFCO-1233zd(E),

78%+/−0.5% by weight HFO-1234ze(E), and

20%+/−0.5% by weight trifluoroiodomethane (CF3I).

Numbered Embodiment 7

The refrigerant as claimed in numbered embodiments 1 to 6 wherein therefrigerant comprises at least about 98.5% by weight of said refrigerantof said three compounds.

Numbered Embodiment 8

A refrigerant consisting essentially of the following three compounds,with each compound being present in the following relative percentagesof:

from 1% by weight to 3% by weight trans-1-chloro-3,3,3-trifluoropropene(HFCO-1233zd(E),

from about 77% by weight to about 83% by weighttrans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E), and

from about 15% by weight to about 21% by weight trifluoroiodomethane(CF3I).

Numbered Embodiment 9

The refrigerant of numbered embodiment 8 wherein the refrigerant ofthree compounds is: from 1% by weight to 3% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E),

from about 77% by weight to about 83% by weighttrans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E), and

from about 18% by weight to about 21% by weight trifluoroiodomethane(CF3I).

Numbered Embodiment 10

The refrigerant of numbered embodiment 8 or numbered embodiment 9wherein the refrigerant of three compounds is from 1% by weight to 3% byweight HFCO-1233zd(E),

from about 77% by weight to about 80% by weight HFO-1234ze(E), and

from about 18% by weight to about 21% by weight trifluoroiodomethane(CF3I).

Numbered Embodiment 11

The refrigerant of any one of numbered embodiments 8 to 10 wherein theHFCO-1233zd(E) is present in an amount of 2%+/−0.5% by weight of thecomposition.

Numbered Embodiment 12

The refrigerant of any one of numbered embodiments 8 to 11 wherein therefrigerant of three compounds is

2%+/−0.5% by weight HFCO-1233zd(E),

about 78% by weight HFO-1234ze(E), and

about 20% by weight trifluoroiodomethane (CF3I).

Numbered Embodiment 13

The refrigerant of any one of numbered embodiments 8 to 12 wherein therefrigerant of three compounds is

2%+/−0.5% by weight HFCO-1233zd(E),

78%+/−0.5% by weight HFO-1234ze(E), and

20%+/−0.5% by weight trifluoroiodomethane (CF3I).

Numbered Embodiment 14

A refrigerant consisting of the following three compounds, with eachcompound being present in the following relative percentages of:

from 1% by weight to 3% by weight trans-1-chloro-3,3,3-trifluoropropene(HFCO-1233zd(E),

from about 77% by weight to about 83% by weighttrans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E), and

from about 15% by weight to about 21% by weight trifluoroiodomethane(CF3I).

Numbered Embodiment 15

The refrigerant of numbered embodiment 14 wherein the refrigerant ofthree compounds is: from 1% by weight to 3% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E),

from about 77% by weight to about 83% by weighttrans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E), and

from about 18% by weight to about 21% by weight trifluoroiodomethane(CF3I).

Numbered Embodiment 16

The refrigerant of numbered embodiment 14 or numbered embodiment 15wherein the refrigerant of three compounds is

from 1% by weight to 3% by weight HFCO-1233zd(E),

from about 77% by weight to about 80% by weight HFO-1234ze(E), and

from about 18% by weight to about 21% by weight trifluoroiodomethane(CF3I).

Numbered Embodiment 17

The refrigerant of any one of numbered embodiments 14 to 16 wherein theHFCO-1233zd(E) is present in an amount of 2%+/−0.5% by weight of thecomposition.

Numbered Embodiment 18

The refrigerant of any one of numbered embodiments 14 to 17 wherein therefrigerant of three compounds is

2%+/−0.5% by weight HFCO-1233zd(E),

about 78% by weight HFO-1234ze(E), and

about 20% by weight trifluoroiodomethane (CF3I).

Numbered Embodiment 19

The refrigerant of any one of numbered embodiments 14 to 18 wherein therefrigerant of three compounds is

2%+/−0.5% by weight HFCO-1233zd(E),

78%+/−0.5% by weight HFO-1234ze(E), and

20%+/−0.5% by weight trifluoroiodomethane (CF3I).

Numbered Embodiment 20

A heat transfer composition comprising a refrigerant of any one ofnumbered embodiments 1 to 19.

Numbered Embodiment 21

The heat transfer composition as claimed in numbered embodiment 20,wherein the refrigerant comprises greater than 40% by weight of thecomposition.

Numbered Embodiment 22

The heat transfer composition as claimed in numbered embodiment 20,wherein the refrigerant comprises greater than 50% by weight of thecomposition.

Numbered Embodiment 23

The heat transfer composition as claimed in numbered embodiment 20,wherein the refrigerant comprises greater than 60% by weight of thecomposition.

Numbered Embodiment 24

The heat transfer composition as claimed in numbered embodiment 20wherein the refrigerant comprises greater than 70% by weight of thecomposition.

Numbered Embodiment 25

The heat transfer composition as claimed in numbered embodiment 20,wherein the refrigerant comprises greater than 80% by weight of thecomposition.

Numbered Embodiment 26

The heat transfer composition as claimed in numbered embodiment 20,wherein the refrigerant comprises greater than 90% by weight of thecomposition.

Numbered Embodiment 27

The heat transfer composition of any one of numbered embodiments 20 to26 wherein said heat transfer composition further comprising astabilizer selected from a diene-based compound and/or a phenol-basedcompound and/or a phosphorus compound and/or a nitrogen compound and/oran epoxide.

Numbered Embodiment 28

The heat transfer composition of any one of numbered embodiments 20 to27 wherein said heat transfer composition further comprising astabilizer selected from a diene-based compounds and/or a phenol-basedcompound and/or a phosphorus compound.

Numbered Embodiment 29

The heat transfer composition of numbered embodiments 27 or 28 whereinthe diene based compound is a terpene selected from the group consistingof terebene, retinal, geranoil, terpinene, delta-3 carene, terpinolene,phellandrene, fenchene, myrcene, farnesene, pinene, nerol, citral,camphor, menthol, limonene, nerolidol, phytol, carnosic acid and vitaminA₁, preferably, farnesene.

Numbered Embodiment 30

The heat transfer composition of numbered embodiment 29 wherein thediene based compound is provided in the heat transfer composition in anamount of from greater than 0, preferably from 0.0001% by weight toabout 5% by weight, more preferably 0.001% by weight to about 2.5% byweight, most preferably from 0.01% to about 1% by weight.

Numbered Embodiment 31

The heat transfer composition of numbered embodiments 27 or 28 whereinthe phosphorus compound is a phosphite or a phosphate compound.

Numbered Embodiment 32

The heat transfer composition of numbered embodiment 31, wherein thephosphite compound is selected from a diaryl, dialkyl, triaryl and/ortrialkyl phosphite, and/or a mixed aryl/alkyl di- or tri-substitutedphosphite, or one or more compounds selected from hindered phosphites,tris-(di-tert-butylphenyl)phosphite, di-n-octyl phophite, iso-octyldiphenyl phosphite, iso-decyl diphenyl phosphite, tri-iso-decylphosphate, triphenyl phosphite and diphenyl phosphite, particularlydiphenyl phosphite.

Numbered Embodiment 33

The heat transfer composition of numbered embodiment 31, wherein thephosphate compounds is selected from a triaryl phosphate, trialkylphosphate, alkyl mono acid phosphate, aryl diacid phosphate, aminephosphate, preferably triaryl phosphate and/or a trialkyl phosphate,particularly tri-n-butyl phosphate.

Numbered Embodiment 34

The heat transfer composition of numbered embodiments 31 to 33 whereinthe phosphorus compound is provided in the heat transfer composition inan amount of greater than 0, preferably from 0.0001% by weight to about5% by weight, more preferably 0.001% by weight to about 2.5% by weight,most preferably from 0.01% to about 1% by weight.

Numbered Embodiment 35

The heat transfer composition of any one of numbered embodiments 27 or28 wherein the stabilizer composition comprises a diene based as claimedin any one of numbered embodiment 29 to 30 and a phosphorous compound asclaimed in any one of numbered embodiments 31 to 34.

Numbered Embodiment 36

The heat transfer composition of numbered embodiment 35 wherein thephosphorous compound is a phosphite compound selected from the groupconsisting of hindered phosphites, tris-(di-tert-butylphenyl)phosphite,di-n-octyl phophite, iso-decyl diphenyl phosphite and diphenylphosphite.

Numbered Embodiment 37

The heat transfer composition of any one of numbered embodiments 35 or36 wherein the phosphorus compounds is provided in the heat transfercomposition in an amount of greater than 0, preferably from 0.0001% byweight to about 5% by weight, more preferably 0.001% by weight to about2.5% by weight, more preferably from 0.01% to about 1% by weight.

Numbered Embodiment 38

The heat transfer composition of any one of numbered embodiments 27 to37 wherein the stabilizer composition comprises farnesene and diphenylphosphite.

Numbered Embodiment 39

The heat transfer composition of any one of numbered embodiments 27 to38, wherein the nitrogen compound is one or more compounds selected fromdinitrobenzene, nitrobenzene, nitromethane, nitrosobenzene, and TEMPO[(2,2,6,6-tetramethylpiperidin-1-yl)oxyl], preferably dinitrobenzene.

Numbered Embodiment 40

The heat transfer composition of any one of numbered embodiments 27 to39 wherein the nitrogen compound is provided in the heat transfercomposition in an amount of greater than 0, preferably from 0.0001% byweight to about 5% by weight, more preferably 0.001% by weight to about2.5% by weight, most preferably from 0.01% to about 1% by weight.

Numbered Embodiment 41

The heat transfer composition of any one of numbered embodiments 27 to40 wherein the phenol compound is BHT.

Numbered Embodiment 42

The heat transfer composition of any one of numbered embodiment 27 to 40wherein the phenol compound is provided in the heat transfer compositionin an amount of greater than 0, preferably from 0.0001% by weight toabout 5% by weight, more preferably 0.001% by weight to about 2.5% byweight, most preferably from 0.01% to about 1% by weight.

Numbered Embodiment 43

The heat transfer composition of any one of numbered embodiments 27 to42 wherein the phenol compound is BHT, wherein said BHT is present in anamount of from about 0.0001% by weight to about 5% by weight based onthe weight of heat transfer composition.

Numbered Embodiment 44

The heat transfer composition any one of numbered embodiments 27 to 43comprising a stabilizer composition comprising farnesene, diphenylphosphite and BHT, wherein the farnesene is provided in an amount offrom about 0.0001% by weight to about 5% by weight based on the weightof the heat transfer composition, the diphenyl phosphite is provided inan amount of from about 0.0001% by weight to about 5% by weight based onthe weight of the heat transfer composition and the BHT is provided inan amount of from about 0.0001% by weight to about 5% by weight based onthe weight of heat transfer composition.

Numbered Embodiment 45

The heat transfer composition of any one of numbered embodiments 20 to44 further comprising a lubricant selected from the group consisting ofpolyol esters (POEs), polyalkylene glycols (PAGs), mineral oil,alkylbenzenes (ABs) and polyvinyl ethers (PVE), more preferably frompolyol esters (POEs), mineral oil, alkylbenzenes (ABs) and polyvinylethers (PVE), particularly from polyol esters (POEs), mineral oil andalkylbenzenes (ABs), most preferably from polyol esters (POEs).

Numbered Embodiment 46

The heat transfer composition of numbered embodiment 45 wherein thelubricant is selected from polyol esters (POEs), polyalkylene glycols(PAGs), mineral oil, alkylbenzenes (ABs) and polyvinyl ethers (PVE).

Numbered Embodiment 47

The heat transfer composition of numbered embodiment 45 wherein thelubricant is selected from polyol esters (POEs), mineral oil,alkylbenzenes (ABs) and polyvinyl ethers (PVE).

Numbered Embodiment 48

The heat transfer composition of numbered embodiment 45 wherein thelubricant is selected from polyol esters (POEs), mineral oil andalkylbenzenes (ABs).

Numbered Embodiment 49

The heat transfer composition of numbered embodiment 45 wherein thelubricant is a polyol ester (POE).

Numbered Embodiment 50

The heat transfer composition of any one of numbered embodiment 45 to 49wherein the lubricant is present in the heat transfer composition in anamount of from 5 to 60% by weight.

Numbered Embodiment 51

The heat transfer composition of any one of numbered embodiment 45 to 49wherein the lubricant is present in the heat transfer composition in anamount of from 30 to 50% by weight.

Numbered Embodiment 52

The heat transfer composition of any one of numbered embodiment 45 to 49wherein the lubricant is present in the heat transfer composition in anamount of from about 10 to 60% by weight of the system using the heattransfer composition.

Numbered Embodiment 53

The heat transfer composition of any one of numbered embodiment 45 to 49wherein the lubricant is present in the heat transfer composition in anamount of from about 20 to about 50% by weight of the system using theheat transfer composition.

Numbered Embodiment 54

The heat transfer composition of any one of numbered embodiment 45 to 49wherein the lubricant is present in the heat transfer composition in anamount of from about 20 to about 40% by weight of the system using theheat transfer composition.

Numbered Embodiment 55

The heat transfer composition of any one of numbered embodiment 45 to 49wherein the lubricant is present in the heat transfer composition in anamount of from about 20 to about 30% by weight of the system using theheat transfer composition.

Numbered Embodiment 56

The heat transfer composition of any one of numbered embodiment 45 to 49wherein the lubricant is present in the heat transfer composition in anamount of from about 30 to about 50% by weight of the system using theheat transfer composition.

Numbered Embodiment 57

The heat transfer composition of any one of numbered embodiment 45 to 49wherein the lubricant is present in the heat transfer composition in anamount of from about 30 to about 40% by weight of the system using theheat transfer composition.

Numbered Embodiment 58

The heat transfer composition of any one of numbered embodiment 45 to 49wherein the lubricant is present in the heat transfer composition in anamount of from about 5 to about 10% by weight of the system using theheat transfer composition.

Numbered Embodiment 59

The heat transfer composition of any one of numbered embodiment 45 to 49wherein the lubricant is present in the heat transfer composition in anamount of from around about 8% by weight of the system using the heattransfer composition.

Numbered Embodiment 60

The heat transfer composition of any one of numbered embodiment 45 to 49wherein the lubricant is present in the heat transfer composition in anamount of from 10 to 60% by weight and wherein the lubricant is a polyolester (POE) lubricant.

Numbered Embodiment 61

The heat transfer composition of any one of numbered embodiments 20 to26 wherein the heat transfer composition consists essentially of therefrigerant as claimed in any one of numbered embodiments 1 to 19.

Numbered Embodiment 62

The heat transfer composition of any one of numbered embodiments 20 to26 wherein the heat transfer composition consist essentially of therefrigerant as claimed in any one of claims 1 to 19 and the stabilizercomposition as claimed in any one of numbered embodiment 27 to 44.

Numbered Embodiment 63

The heat transfer composition of any one of numbered embodiments 20 to26 wherein the heat transfer composition consist essentially of therefrigerant as claimed in any one of numbered embodiment 1 to 19, thestabilizer composition as claimed in any one of numbered embodiments 27to 44 and the lubricant as claimed in any one of numbered embodiment 45to 60.

Numbered Embodiment 64

The heat transfer composition of any one of numbered embodiments 20 to63 having a Global Warming Potential (GWP) of less than 150.

Numbered Embodiment 65

The heat transfer composition of any one of numbered embodiments 20 to64 having an Ozone Depletion Potential (ODP) of not greater than 0.05,preferably 0.02, more preferably about zero.

Numbered Embodiment 66

A low temperature refrigeration system containing a refrigerant of anyone of numbered embodiments 1-19 or a heat transfer composition of anyone of numbered embodiments to 64.

Numbered Embodiment 67

A medium temperature refrigeration system containing a refrigerant ofany one of numbered embodiments 1-19 or a heat transfer composition ofany one of numbered embodiments 20 to 64.

Numbered Embodiment 68

A heat pump containing a refrigerant of any one of numbered embodiments1-19 or a heat transfer composition of any one of numbered embodiments20 to 64.

Numbered Embodiment 69

A dehumidifier containing a refrigerant of any one of numberedembodiments 1-19 or a heat transfer composition of any one of numberedembodiments 20 to 64.

Numbered Embodiment 70

A vending machine containing a refrigerant of any one of numberedembodiments 1-19 or a heat transfer composition of any one of numberedembodiments 20 to 64.

Numbered Embodiment 71

A chiller containing a refrigerant of any one of numbered embodiments1-19 or a heat transfer composition of any one of numbered embodiments20 to 64.

Numbered Embodiment 72

A refrigerator containing a refrigerant of any one of numberedembodiments 1-19 or a heat transfer composition of any one of numberedembodiments 20 to 64.

Numbered Embodiment 73

A freezer containing a refrigerant of any one of numbered embodiments1-19 or a heat transfer composition of any one of numbered embodiments20 to 64.

Numbered Embodiment 74

A cascade refrigeration system containing a refrigerant of any one ofnumbered embodiments 1-19 or a heat transfer composition of any one ofnumbered embodiments to 64.

Numbered Embodiment 75

A refrigerant comprising at least about 97% by weight of the followingfour compounds, with each compound being present in the followingrelative percentages:

from 1% by weight to 2%+/−0.5% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),

from about 73% by weight to about 87% by weighttrans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 4.4%+/−0.5% by weight1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and

from about 6.6% by weight to about 20.6% by weight trifluoroiodomethane(CF₃I).

Numbered Embodiment 76

A refrigerant comprising at least about 98.5% by weight of the followingthree compounds, with each compound being present in the followingrelative percentages:

from 1% by weight to 2%+/−0.5% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),

from about 73% by weight to about 87% by weighttrans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 4.4%+/−0.5% by weight1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and

from about 6.6% by weight to about 20.6% by weight trifluoroiodomethane(CF3I).

Numbered Embodiment 77

A refrigerant comprising at least about 99.5% by weight of the followingthree compounds, with each compound being present in the followingrelative percentages:

from 1% by weight to 2%+/−0.5% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),

from about 73% by weight to about 87% by weighttrans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 4.4%+/−0.5% by weight1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and

from about 6.6% by weight to about 20.6% by weight trifluoroiodomethane(CF3I).

Numbered Embodiment 78

A refrigerant consisting essentially of the following four compounds,with each compound being present in the following relative percentages:

from 1% by weight to 2%+/−0.5% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),

from about 73% by weight to about 87% by weighttrans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 4.4%+/−0.5% by weight1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and

from about 6.6% by weight to about 20.6% by weight trifluoroiodomethane(CF₃I).

Numbered Embodiment 79

A refrigerant comprising at least about 98.5% by weight of the followingfour compounds, with each compound being present in the followingrelative percentages:

2%+/−0.5% by weight trans-1-chloro-3,3,3-trifluoropropene(HFCO-1233zd(E)),

about 84% by weight trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),

4.4%+/−0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and

about 9.6% by weight trifluoroiodomethane (CF3I).

Numbered Embodiment 80

trifluoropropene (HFCO-1233zd(E)),

about 84% by weight trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),

4.4%+/−0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and

about 9.6% by weight trifluoroiodomethane (CF3I).

Numbered Embodiment 81

A refrigerant consisting of the following four compounds, with eachcompound being present in the following relative percentages:

2%+/−0.5% by weight trans-1-chloro-3,3,3-trifluoropropene(HFCO-1233zd(E)),

about 84% by weight trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),

4.4%+/−0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and

about 9.6% by weight trifluoroiodomethane (CF3I).

Numbered Embodiment 82

A refrigerant comprising at least about 98.5% by weight of the followingfour compounds, with each compound being present in the followingrelative percentages:

2%+/−0.5% by weight trans-1-chloro-3,3,3-trifluoropropene(HFCO-1233zd(E)),

84%+/−0.5% by weight trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),

4.4%+/−0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and

9.6%+/−0.5% by weight trifluoroiodomethane (CF3I).

Numbered Embodiment 83

A refrigerant consisting essentially of the following four compounds,with each compound being present in the following relative percentages:

2%+/−0.5% by weight trans-1-chloro-3,3,3-trifluoropropene(HFCO-1233zd(E)),

84%+/−0.5% by weight trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),

4.4%+/−0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and

9.6%+/−0.5% by weight trifluoroiodomethane (CF3I).

Numbered Embodiment 84

A refrigerant comprising consisting of the following four compounds,with each compound being present in the following relative percentages:

2%+/−0.5% by weight trans-1-chloro-3,3,3-trifluoropropene(HFCO-1233zd(E)),

84%+/−0.5% by weight trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),

4.4%+/−0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and

9.6%+/−0.5% by weight trifluoroiodomethane (CF3I).

Numbered Embodiment 85

A heat transfer composition comprising a refrigerant of any one ofnumbered embodiments 75 to 84.

Numbered Embodiment 86

The heat transfer composition as claimed in numbered embodiment 85,wherein the refrigerant comprises greater than 40% by weight of thecomposition.

Numbered Embodiment 87

The heat transfer composition as claimed in numbered embodiment 85,wherein the refrigerant comprises greater than 50% by weight of thecomposition.

Numbered Embodiment 88

The heat transfer composition as claimed in numbered embodiment 85,wherein the refrigerant comprises greater than 60% by weight of thecomposition.

Numbered Embodiment 89

The heat transfer composition as claimed in numbered embodiment 85wherein the refrigerant comprises greater than 70% by weight of thecomposition.

Numbered Embodiment 90

The heat transfer composition as claimed in numbered embodiment 85,wherein the refrigerant comprises greater than 80% by weight of thecomposition.

Numbered Embodiment 91

The heat transfer composition as claimed in numbered embodiment 85,wherein the refrigerant comprises greater than 90% by weight of thecomposition.

Numbered Embodiment 92

The heat transfer composition of any one of numbered embodiments 85 to91 wherein said heat transfer composition further comprises a stabilizerselected from a diene-based compound and/or a phenol-based compoundand/or a phosphorus compound and/or a nitrogen compound and/or anepoxide.

Numbered Embodiment 93

The heat transfer composition of any one of numbered embodiments 85 to91 wherein said heat transfer composition further comprises a stabilizerselected from a diene-based compounds and/or a phenol-based compoundand/or a phosphorus compound.

Numbered Embodiment 94

The heat transfer composition of numbered embodiments 92 or 93 whereinthe diene based compound is a terpene selected from the group consistingof terebene, retinal, geranoil, terpinene, delta-3 carene, terpinolene,phellandrene, fenchene, myrcene, farnesene, pinene, nerol, citral,camphor, menthol, limonene, nerolidol, phytol, carnosic acid and vitaminA₁, preferably, farnesene.

Numbered Embodiment 95

The heat transfer composition of numbered embodiment 94 wherein thediene based compound is provided in the heat transfer composition in anamount of from greater than 0, preferably from 0.0001% by weight toabout 5% by weight, more preferably 0.001% by weight to about 2.5% byweight, most preferably from 0.01% to about 1% by weight.

Numbered Embodiment 96

The heat transfer composition of numbered embodiments 85 to 95 wherein aphosphorous compound is present and wherein the phosphorus compound is aphosphite or a phosphate compound.

Numbered Embodiment 97

The heat transfer composition of numbered embodiment 96, wherein thephosphite compound is selected from a diaryl, dialkyl, triaryl and/ortrialkyl phosphite, and/or a mixed aryl/alkyl di- or tri-substitutedphosphite, or one or more compounds selected from hindered phosphites,tris-(di-tert-butylphenyl)phosphite, di-n-octyl phophite, iso-octyldiphenyl phosphite, iso-decyl diphenyl phosphite, tri-iso-decylphosphate, triphenyl phosphite and diphenyl phosphite, particularlydiphenyl phosphite.

Numbered Embodiment 98

The heat transfer composition of numbered embodiment 96, wherein thephosphate compounds is selected from a triaryl phosphate, trialkylphosphate, alkyl mono acid phosphate, aryl diacid phosphate, aminephosphate, preferably triaryl phosphate and/or a trialkyl phosphate,particularly tri-n-butyl phosphate.

Numbered Embodiment 99

The heat transfer composition of numbered embodiments 97 or 98 whereinthe phosphorus compound is provided in the heat transfer composition inan amount of greater than 0, preferably from 0.0001% by weight to about5% by weight, more preferably 0.001% by weight to about 2.5% by weight,most preferably from 0.01% to about 1% by weight.

Numbered Embodiment 100

The heat transfer composition of any one of numbered embodiments 97 or98 wherein the stabilizer composition comprises a diene based as claimedin any one of numbered embodiment 29 to 30 and a phosphorous compound asclaimed in any one of numbered embodiments 31 to 34.

Numbered Embodiment 101

The heat transfer composition of numbered embodiment 100 wherein thephosphorous compound is a phosphite compound selected from the groupconsisting of hindered phosphites, tris-(di-tert-butylphenyl)phosphite,di-n-octyl phophite, iso-decyl diphenyl phosphite and diphenylphosphite.

Numbered Embodiment 102

The heat transfer composition of any one of numbered embodiments 100 or101 wherein the phosphorus compounds is provided in the heat transfercomposition in an amount of greater than 0, preferably from 0.0001% byweight to about 5% by weight, more preferably 0.001% by weight to about2.5% by weight, more preferably from 0.01% to about 1% by weight.

Numbered Embodiment 103

The heat transfer composition of any one of numbered embodiments 92 to102 wherein the stabilizer composition comprises farnesene and diphenylphosphite.

Numbered Embodiment 104

The heat transfer composition of any one of numbered embodiments 92 to103, wherein the nitrogen compound is one or more compounds selectedfrom dinitrobenzene, nitrobenzene, nitromethane, nitrosobenzene, andTEMPO [(2,2,6,6-tetramethylpiperidin-1-yl)oxyl], preferablydinitrobenzene.

Numbered Embodiment 105

The heat transfer composition of any one of numbered embodiments 92 to104 wherein the nitrogen compound is provided in the heat transfercomposition in an amount of greater than 0, preferably from 0.0001% byweight to about 5% by weight, more preferably 0.001% by weight to about2.5% by weight, most preferably from 0.01% to about 1% by weight.

Numbered Embodiment 106

The heat transfer composition of any one of numbered embodiments 92 to105 wherein the phenol compound is BHT.

Numbered Embodiment 107

The heat transfer composition of any one of numbered embodiment 92 to105 wherein the phenol compound is provided in the heat transfercomposition in an amount of greater than 0, preferably from 0.0001% byweight to about 5% by weight, more preferably 0.001% by weight to about2.5% by weight, most preferably from 0.01% to about 1% by weight.

Numbered Embodiment 108

The heat transfer composition of any one of numbered embodiments 92 to105 wherein the phenol compound is BHT, wherein said BHT is present inan amount of from about 0.0001% by weight to about 5% by weight based onthe weight of heat transfer composition.

Numbered Embodiment 109

The heat transfer composition any one of numbered embodiments 92 to 105comprising a stabilizer composition comprising farnesene, diphenylphosphite and BHT, wherein the farnesene is provided in an amount offrom about 0.0001% by weight to about 5% by weight based on the weightof the heat transfer composition, the diphenyl phosphite is provided inan amount of from about 0.0001% by weight to about 5% by weight based onthe weight of the heat transfer composition and the BHT is provided inan amount of from about 0.0001% by weight to about 5% by weight based onthe weight of heat transfer composition.

Numbered Embodiment 110

The heat transfer composition of any one of numbered embodiments 95 to109 further comprising a lubricant selected from the group consisting ofpolyol esters (POEs), polyalkylene glycols (PAGs), mineral oil,alkylbenzenes (ABs) and polyvinyl ethers (PVE), more preferably frompolyol esters (POEs), mineral oil, alkylbenzenes (ABs) and polyvinylethers (PVE), particularly from polyol esters (POEs), mineral oil andalkylbenzenes (ABs), most preferably from polyol esters (POEs).

Numbered Embodiment 111

The heat transfer composition of numbered embodiment 110 wherein thelubricant is selected from polyol esters (POEs), polyalkylene glycols(PAGs), mineral oil, alkylbenzenes (ABs) and polyvinyl ethers (PVE).

Numbered Embodiment 112

The heat transfer composition of numbered embodiment 110 wherein thelubricant is selected from polyol esters (POEs), mineral oil,alkylbenzenes (ABs) and polyvinyl ethers (PVE).

Numbered Embodiment 113

The heat transfer composition of numbered embodiment 110 wherein thelubricant is selected from polyol esters (POEs), mineral oil andalkylbenzenes (ABs).

Numbered Embodiment 114

The heat transfer composition of numbered embodiment 110 wherein thelubricant is a polyol ester (POE).

Numbered Embodiment 115

The heat transfer composition of any one of numbered embodiment 110 to114 wherein the lubricant is present in the heat transfer composition inan amount of from 5 to 60% by weight.

Numbered Embodiment 116

The heat transfer composition of any one of numbered embodiment 110 to114 wherein the lubricant is present in the heat transfer composition inan amount of from 30 to 50% by weight.

Numbered Embodiment 117

The heat transfer composition of any one of numbered embodiment 110 to114 wherein the lubricant is present in the heat transfer composition inan amount of from about 10 to 60% by weight of the system using the heattransfer composition.

Numbered Embodiment 118

The heat transfer composition of any one of numbered embodiment 110 to114 wherein the lubricant is present in the heat transfer composition inan amount of from about 20 to about 50% by weight of the system usingthe heat transfer composition.

Numbered Embodiment 119

The heat transfer composition of any one of numbered embodiment 110 to114 wherein the lubricant is present in the heat transfer composition inan amount of from about 20 to about 40% by weight of the system usingthe heat transfer composition.

Numbered Embodiment 120

The heat transfer composition of any one of numbered embodiment 110 to114 wherein the lubricant is present in the heat transfer composition inan amount of from about 20 to about 30% by weight of the system usingthe heat transfer composition.

Numbered Embodiment 121

The heat transfer composition of any one of numbered embodiment 110 to114 wherein the lubricant is present in the heat transfer composition inan amount of from about 30 to about 50% by weight of the system usingthe heat transfer composition.

Numbered Embodiment 122

The heat transfer composition of any one of numbered embodiment 110 to114 wherein the lubricant is present in the heat transfer composition inan amount of from about 30 to about 40% by weight of the system usingthe heat transfer composition.

Numbered Embodiment 123

The heat transfer composition of any one of numbered embodiment 110 to114 wherein the lubricant is present in the heat transfer composition inan amount of from about 5 to about 10% by weight of the system using theheat transfer composition.

Numbered Embodiment 124

The heat transfer composition of any one of numbered embodiment 110 to114 wherein the lubricant is present in the heat transfer composition inan amount of from around about 8% by weight of the system using the heattransfer composition.

Numbered Embodiment 125

The heat transfer composition of any one of numbered embodiment 110 to114 wherein the lubricant is present in the heat transfer composition inan amount of from 10 to 60% by weight and wherein the lubricant is apolyol ester (POE) lubricant.

Numbered Embodiment 126

The heat transfer composition of any one of numbered embodiments 95 to101 wherein the heat transfer composition consists essentially of therefrigerant as claimed in any one of numbered embodiments 75 to 94.

Numbered Embodiment 127

The heat transfer composition of any one of numbered embodiments 75 to94 wherein the heat transfer composition consist essentially of therefrigerant as claimed in any one of claims 75 to 84 and the stabilizercomposition as claimed in any one of numbered embodiment 92 to 109.

Numbered Embodiment 128

The heat transfer composition of any one of numbered embodiments 92 to109 wherein the heat transfer composition consist essentially of therefrigerant as claimed in any one of numbered embodiment 75 to 84, thestabilizer composition as claimed in any one of numbered embodiments 92to 109 and the lubricant as claimed in any one of numbered embodiment110 to 125.

Numbered Embodiment 129

The heat transfer composition of any one of numbered embodiments 85 to128 having a Global Warming Potential (GWP) of less than 150.

Numbered Embodiment 130

The heat transfer composition of any one of numbered embodiments 85 to128 having an Ozone Depletion Potential (ODP) of not greater than 0.05,preferably 0.02, more preferably about zero.

Numbered Embodiment 131

A low temperature refrigeration system containing a refrigerant of anyone of numbered embodiments 75-84 or a heat transfer composition of anyone of numbered embodiments 85 to 128.

Numbered Embodiment 132

A medium temperature refrigeration system containing a refrigerant ofany one of numbered embodiments 75-84 or a heat transfer composition ofany one of numbered embodiments 85 to 128.

Numbered Embodiment 133

A heat pump containing a refrigerant of any one of numbered embodiments75-84 or a heat transfer composition of any one of numbered embodiments85 to 128.

Numbered Embodiment 134

A dehumidifier containing a refrigerant of any one of numberedembodiments 75-84 or a heat transfer composition of any one of numberedembodiments 84 to 128.

Numbered Embodiment 135

A vending machine containing a refrigerant of any one of numberedembodiments 75-84 or a heat transfer composition of any one of numberedembodiments 84 to 128.

Numbered Embodiment 136

A chiller containing a refrigerant of any one of numbered embodiments75-84 or a heat transfer composition of any one of numbered embodiments84 to 128.

Numbered Embodiment 137

A refrigerator containing a refrigerant of any one of numberedembodiments 75-84 or a heat transfer composition of any one of numberedembodiments 85 to 128.

Numbered Embodiment 138

A freezer containing a refrigerant of any one of numbered embodiments75-49 or a heat transfer composition of any one of numbered embodiments85 to 128.

Numbered Embodiment 139

A cascade refrigeration system containing a refrigerant of any one ofnumbered embodiments 75-84 or a heat transfer composition of any one ofnumbered embodiments 85 to 128.

Although the invention has been described with reference to preferredembodiments, it will be understood by those skilled in the art thatvarious changes may be made and equivalents substituted for elementsthereof without departing from the scope of the invention. In addition,many modifications may be made to adapt to a particular situation ormaterial to the teachings of the invention with departing from theessential scope thereof. Therefore, it 15 is intended that the inventionnot be limited to the particular embodiments disclosed, but that theinvention will include all embodiments falling within the scope of theappended claims or any claims added later.

1. A refrigerant comprising at least about 97% by weight of thefollowing four compounds, with each compound being present in thefollowing relative percentages: from 1% by weight to 2%+/−0.5% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)), from about 73%by weight to about 87% by weight trans-1,3,3,3-tetrafluoropropene(HFO-1234ze(E)), 4.4%+/−0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane(HFC-227ea), and from about 6.6% by weight to about 20.6% by weighttrifluoroiodomethane (CF₃I).
 2. A heat transfer composition comprising arefrigerant of claim
 1. 3. The heat transfer composition of claim 2further comprising a lubricant.
 4. The heat transfer composition ofclaim 2 further comprising a stabilizer.
 5. The heat transfercomposition of claim 3 further comprising a stabilizer.
 6. A refrigerantcomprising at least about 97% by weight of the following threecompounds, with each compound being present in the following relativepercentages of: from 1% by weight to 3% by weighttrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E), from about 77% byweight to about 83% by weight trans-1,3,3,3-tetrafluoropropene(HFO-1234ze(E), and from about 15% by weight to about 21% by weighttrifluoroiodomethane (CF3I).
 7. A heat transfer composition comprising arefrigerant of claim
 1. 8. The heat transfer composition of claim 2further comprising a lubricant.
 9. The heat transfer composition ofclaim 2 further comprising a stabilizer.
 10. The heat transfercomposition of claim 3 further comprising a stabilizer.